Skip to main content
Internet Archive's 25th Anniversary Logo

Full text of "Year-Book of Pharmacy, comprising abstracts of papers relating to pharmacy, materia medica and chemistry contributed to British and foreign journals with Transactions of the British Pharmaceutical Conference"

See other formats


COLLEGE  OF  r  HARriACY 

44    GERRARD  ST.  E. 
TORONTO, 


I 


ONTARIO 

COLLEGE  OF  FHARflACY 

44    GERRARD  ST.  E. 
TORONTO, 


♦ 


EH    :? 

Q     I 

<     t 

•'I  no   o 

ia<j.g 

w    « 

n,  H  •" 
FhOOh 

«  ^    o 

a^  I 

mW.2 

go5 


&< « s 

05    P   o 

/3  00  -2 

O  rH    o 
00         TS 

'-'     M     CO 


£P  ^  i.  o  S  -^  s 


&o  ^-i.S 


w 

o 

o 

2> 

55 

£ 

CO 

5 

P3 

o 

;2; 

-s 

co- 
co 

CO 

00 
r-l 

1 

w 

00 

.-I 

= 

« 

-o 

"   P    to 


r'  w  S.2'■S 
h  O  o  s  = 

s  z  2  -2  '^ 


00  6 


-q   cij  i- 

5cq  - 


^^-' 


"-> 


«       I 

CO  o  ~ 
OD  H  S 
t-l    ffi    b 

'^  c-  ? 

_^'00  -3 
CD  '"'  § 
00  S 

I— I      .    ~ 

W  J 

.    O  S 
J    p    ° 

(D  C  g 
-<  S  s 
o  p  -s 
^  a  s 

eO  00  -J 
CO  ^  a 
00        -c 


&* 


fe 


03 

«^ 

si 

ace  •" 

s" 


CO  ., 
1— (    . 

..OQ 

aJQ3 

"3  CO 

Ma 


CO  t^ 

00  00 


o  a 


1-2  a  I  g 

1  a '-'  s  „ 


-.^  a  o  ^  ^►^  a  ©L 
.9  '^ 


g 


9  -= 


.S  ^  o  ^  d  i  o 

C   <S  <«J         "    o    m 


^J3  .5  ^ 


!x  .: 


u 


CD  ce    rl    J=^  O  n:j 

W    03    fl 


9  f^ 


^  p.  a 

•^  CO       H  ^  ® 


*   r— 


fi,  o  o 


(C 

m    03 

a 

"S  "".2 

p 

03    &D^ 

Sm     p    -*J 

p 

to  "C  «« 

■^ 

^    S    O 

o 

03 

2f9  J 


•  «  to  a) 

a  a  a 

2  0'43 

a  o  *^ 


>i 


^pq  a     ^ 


S  5  * 

m   2    11 

©-*!  " 

>^   o  ^ 

•    to    t>-. 

s  p  a 
af^  fl 

a  fc^-g 

"    03    &i 

°    £    « 
to   o   S 


58  P  <u 
o  o  -a 


a     W 


W-^ 


O  'S 

CD  -"  a 

QJ  '?  Pi 
O  S  * 
--&:>> 
&<)  i-i  '^ 

3     O     C8 

Ph  O    03 


11    o 

'a  a  i-l  oi 


p,    <3 


IB  rrS 

.E:  o 


a  00 


.2  2  ":  a 

<U    h  1^    6D  6D 

"  ^'a  -B  2 

oi'  S  2  S  .15  £ 


■9"  >-. 


OS    o 


^    sc  §  tf-g  a  -^  S 

^       e8da'-'"tea 
■Ts       S  J?  — 1  •_  i.>,  "^  P 


Pi 


"^■^5  2S, 


CO  P-H  a  t.  CO  § 


k>^ 


r;^      O)  t^     CO    -t-> 

aw  a,  >,^ 


2-a 


fl-.S    to'   >-    d    <D 
0-3.2    ®-^ 

p.1^  a    ' 
•^  g  HH  a 

CO    ^    to  _r) 

pO  tn  o)  rs 

S  -a  l> 


"  —S-'^t'D 


W 


aXo^s 
g  cj  1^  o  S 


,.S   1/3  *       9-. a 


^      .  _  ^  1  Q  *  ^-2 

£  ■3t-^'.g.9's  |-s 

a  ="  o  W      — -u  w  <" 

ft'  S  -p  a  '^  « 


a  cl  a 


Pife 


^: 


y  o 


^.9  ^  §  J 

O    O    <»  i-s  CO 

O    O  -*f  I 

M  '5  a  ^  •:3 
I   p-i— 1 


CO  "^ 


J  00 

a  CD  .*j  o  o    - 
G  2  S  t~  ■*  •" 


^  a  P-  2  00 


a  >* 


'  ^  -^ 


'«'23 


a     IS 

2  S-S  I 


Sa^^  W.^^^-SSS^-^ .2.275 

JJ.CO--      ~-     - 


P-in   2   ^     S 


a  °s 

o  ^-9 

-t."   c:i   a 

m     CS     p. 


p  .-l^  „  « 

&=    ^    §    o 


CO  _o    » 

flSffi2'"Saa 
oS^^aQrOcDy 
m2a<i>yaS'" 
cu-gapHgaarQ 
tj  Ph  a  M  a  "'^  .    ri 

p<^  g  -g  s  a  it  9 

03    to    s    a    "K  _a  't! 

a  2  g  §35  o^ 

S    ^C    .  n,    g  _co   g 

g  2  s  ec  s  -s  ^  a 


^   m 

^  ^ 


c  s.2^ 


g  O   c3  ^ 

<I>     O     C     r- 


■"    Ci    ft 

a   ^   eS 


a  03  ^ 

0  2  r 

.9  -a  e 

.t!H  o 


a  Fs 

■^  2i  S 
a. 2  a 


02  aj  -o-s  ft-^ 

r-i  a-g^-aNns  "  o  a 

03  S.-ftH  ^  g-jfpq-^' 

msB*    «>aj2-'2 


ft  <u 


^  a  ftg-S^*^  o  .  - 
S  «  &S^O  a^  S^ 


S  5  -^  -S  a 
O!  '73  g  "  "" 


^cj     -     tj     y- 


J  ^  §  £^.9 ' 


•2   5 

a 


:is  -73 


a  <»  S 

"    ^S  a 

ft  <i> 

go  to  a  -t3  .a  »  ^,  a 
h-ioPoioa^P 

■;:!    (^  a  . 

»  to  a 


.■TS 


0=  2  S  S'S  —  -^-i 

£  ^  <u  o  a  »  . 

O    ^  S»-.'5    (U    O    c,  ^ 

"^       ^  a  f^t^  o 

-..     -,-«<SCJ(D— !  "^gS 

_     CD  ?^ 

s  -p 


•r;  f^    03    6XJ  03 


a  ■-■'3  .2fO 

(D    CO 


S  a 


O     r-* 


H  .r 


a  «  6  -^  '-^  ^  ■  2  ° 

*  e^^  C    <"    S;    ft3 

g  o  o-jSr^  S-r  — 


a  2 


o  Ph  H   ^  S  ■"  '? 
t^.o 


m     -jspq 


*§  S3  a 

a3   00   a 


Price  10s.;  or  post  free  10s.  6d. 
Members  arc  entitled  to  one  copy  ;  additional  copies,  post  free,  7«.  6d. 

YEAR-BOOK  OF  PHARMACY 

COMPRISING 

ABSTRACTS  OF  PAPERS 

RELATING    TO 

PHARMACY,  MATERIA  MEDICA,  AND  CHEMISTRY 

CONTEIBUTED  TO  BRITISH  AND  FOREIGN  JOURNALS, 
PROM  JULY  1,  1876,  TO  JUNE  30, 


1877. 

WITH  THE  Toronto    ' 

TRANSACTIONS 


BRITISH    PHARMACEUTICAL 
CONFERENCE 

AT    THE 

FOURTEENTH    ANNUAL    MEETING 

HELD    IN 

PLYMOUTH, 
AUGUST,  1877. 


LONDON: 
J.  &  A    CHURCHILL,  11,  NEW  BURLINGTON  STREET. 

MDCCCLXXVII. 


Bntisif)  pftarmamitiral  Conferenre, 


YEAR-BOOK   OF    PHARMACY 

Committee  of  Publication. 

W.  W.  STODDART,  F.C.S.,  F.G.S. 

MICHAEL  CARTEIGHE,  F.C.S. 

THOS.  B.  GROVES,  F.C.S. 

F.  B.  BENGER,    F.C.S. 

Prof.  ATTFIELD,  Ph.D.,  F.C.S.,  Secretary. 

Editor  of  the  Transactions  of  the  Conference. 
Prof.  ATTFIELD,  Ph.D.,  F.C.S. 


BRITISH  PHARMACEUTICAL  CONFERENCE. 


OFFICERS  FOR  1877-78. 

President. 
G.  F.  SCHACHT,  F.C.S.,  Clifton,  Bristol. 

Vice-Presidents, 
Who  have  filled  the  office  of  President. 

Prof.  BENTLEY,  F.L.S.,  M.R.C.S.,  London. 
W.  W.  STODDART,  F.C.S.,  F.G.S.,  Bristol. 
H.  B.  BRADY,  F.R.S.,  Newcastle-on-Tyne. 
THOMAS  B.  GROVES,  F.C.S.,  Weymouth. 
Prof.  REDWOOD,  Ph.D.,  F.C.S.,  London. 

Vice-Presidents. 

Prof.  TICHBORNE,  F.C.S.,  Dublin.   ONTARIO 
R.  REYNOLDS,  F.C.S.,  Leeds.  r.  „  .  .  ,^ 

R.  W.  PRING,L.A.H.D.,BfWpt.|  p.QP    Qp    PHAR^iAC 
J.  WILLIAMS,  F.C.S.,  LoMbrfr '""-''-    ^^^     ' 

44    GERRARD  ST.  E 
Treasurer.  -rr~\ 

C.  BKIN,  F.C.S.,  8,  Argyle  Street,  BaThP  RO  NTO  , 

Genbrax  Secbetaries. 

Prof.  ATTPIELD,  Ph.D.,  P.C.S.,  17,  Bloomsbury  Sq.,  London,  W.G. 
F.  BADEN  BENGER,  F.C.S.,  7,  Exchange  Street,  Manchester. 

Assistant  Secretab,t. 
A.  SENIBR,  M.D.,  F.C.S.,  17,  Bloomsbury  Square,  London,  W.G. 

LocAi  Secretary. 
W.  HAYES,  Dublin. 

Other  Members  of  the  Executive  Committee,  1877-78. 
M.  CARTEIGHE,  F.C.S.,  London. 

A.  P.  BALKWILL,  Plymouth. 
N.  H.  DRAPER,  F.C.S.,  Dublin. 

B.  S.  PROCTOR,  Newcastle-on-Tyne. 
E.  SMITH,  F.C.S.,  Torquay. 

W.  A.  TILDEN,  D.Sc,  F.C.S.,  Clifton. 

C.  UMNEY,  F.C.S.,  London. 
J.  T.  HOLMES,  Dublin. 

J.  C.  THRESH,  F.C.S.,  Buxton. 

Auditors. 
S.  B.  TURNEY,  Plymouth.  W.  ALLEN,  Dublin. 

These  Officers  collectively  constitute  the  Executive  Gommittee.    Three  re- 
tire  annually,  the  remainder  being  eligible  for  re-election. 


QQ 

O 

Q     «? 

a 

3 
»-5 

fa 

O               O 

.  a 

d:2 

03 

d 
fa 

S  2        , 

z"     «              £ 

=i"     =     5           2     ui 

s. 

>• 

iJ 

g        fa 

a   faB 

o 

o 
o 

d 

< 

o 
en 

K     w     5 
a    K    M 

1  §i 

«cp 

S      £      ^        •      S      « 

>H     S     5     5     S     <     « 
00      3      S      -"J      5      iJ      IS 

5     «     5     g      z     !^     5 

C5     fa     O     Ph     w     -^     W 

•-5 

^ 

HJ         t-i         fa 

^   Bn' 

►-5 

tn'       P3       a       h,"       -li       pj       ^ 

^-*— ^ 

-^ 

-' ■ ^ 

-' ^ 

-^ 

CC                           02 

02       «?^ 

d       ^.^. 
r"        fafa 

d  . 

r/j 

9         029       q 

02^-aJ     02     h"^-        o^Wcq 

w, 

d^ 

fa        "^ 

4  SI 

O 

dod^d    i^g     j9^9 

2 

.  o 

5  -^ 

02  ~'^ma^^ 

•  Q  z  r-  r-  s 

fa-gfa-ofa\;a-o      j^faJfa 
O^S^P^^dfa^^^^ 

1 

111 

fa  p  -<fa 

da 
5^ 

Ed 

-c» 

P^Oh 

^t-iCQ^P^^l-iHi^H'-J'-Jl-J 

^i-ifat-;OH;ofaWQ<Ji-i(^'-i 

1 

02 

•«S 

cc    . 

/: 

02-02^^0202^     -OlJ-odiv;"? 

d^-dgdd^^.d^-d'^-o 

fa9fa-^fafal^9^9£^«fe 
Oj'^^fa^^fa^^^     .fe'^^fa'^^l'^^ 

fa  g  :^  §  §  g  ^  1  :^  g  :^  g  1  g 

% 

j2 

h3=» 

J  02 

^imai 

CO 

a 

-fa 

K  on 

Z  < 

S,SS'4faH 

<!;  y  pfa    -fa 

o 
fa      z 

ii  5  <  h; 
O     .  ca    • 

z 

^  e  s    _S    . 
C  Z  Z  s  ,^  H 

«"gw£wgwgagMg-g 

ts 

2^ 

M  <  <  o  S  o 

^.aw^fa^ 

^^ 

Zp5HP5HP5WP5HP^W«'SP5 

i 

(t,Q|i,PQQPH;p3»^ 

JSKh^W 

H^W 

i^p^HP3HP^E-lp^f-P3eip3PHp3 

02 

m 

.       02 

CQ       02       ^ 

02 

d 

02          ■          ■          ■ 

;  :  2  s «?  -i  02 

02     oj     ^       .    o     q     H 

ei 

^ 

>A 

^        HJ        ^ 

fa   p^ 

fa 

a 

D 

Z 

1— 1 

^ 

E^ 

U* 

fa        fa         g 

>•"     >""     2 

H        M        g 

Ph      fa      Q 

H 

P3     «      „-     S     fe     ^     fa 

1 

z 

■«! 

Q 

> 

z 

■<! 
H 

Q 

c 

Q 
O 
E- 
02 

S    S    1    5    1    1    1 

pq     p:     «           P3     p3    ro 

z 

w 

z 

w 

^ 

^ 

•       •     §     §     S     2    \^ 
W     W     H     H     fa     Ph     o 

a 

a 

s-l 

5 

to 

1  t  % 
■f  1  1 

^     O     ;z; 

.a 
3 

^    1    1    1     §>    1    ;3 

•C      g      5     -E      ^      >•     5 

m    n    H^i    P5    c5    fa    P 

c 

^ 

\a 

1-1         ^         pH 

CS       o 

^ 

efl      eo      ■^      >o      «0      t-      00 

^ 

f^ 

«        00 

1-t          i-H 

CO 

00        00        00        CO        00        00        00 

02 

fao  • 

Q    -fa 

fa  kJ  a 

-  O  O 

Q  Z  Z 

1-5   >>  K 

K  apq 

F-  c  a 
.  i  < 

CO 

fap^fa 


05 

z  w^C: 
a  Bi 


O 


o 
fa 

02  a 

fa  goo 
>:o2  0 

Sfa^ 

•  sj  ^ 

P5  OH 

aod 

00  00  00 


BO  f* 


THE 

BRITISH  PHARMACEUTICAL  CONFERENCE. 

AN  ORGANIZATION  ESTABLISHED  IN  1863  FOR  THE  ENCOURAGE- 
MENT OF  PHARMACEUTICAL  RESEARCH,  AND  THE  PROMOTION  OF 
FRIENDLY  INTERCOURSE  AND  UNION  AMONGST  PHARMACISTS. 


The  most  important  ways  in  which  a  member  can  aid  the  objects  of 
the  Conference  are  by  suggesting  subjects  for  investigation,  working 
upon  subjects  suggested  by  himself  or  by  others,  contributing  infor- 
mation tending  to  throw  light  on  questions  relating  to  adulterations 
and  impurities,  or  collecting  and  forwarding  specimens  whose  exa- 
mination would  afford  similar  information.  Personal  attendance  at 
the  yearly  gatherings,  or  the  mere  payment  of  the  annual  subscrip- 
tion, will  also  greatly  strengthen  the  hands  of  the  executive. 

A  list  of  subjects  suggested  for  research,  is  sent  to  members  early 
in  the  year.  Resulting  papers  are  read  at  the  annual  meeting  of  the 
members ;  but  new  facts  that  are  discovered  during  an  investigation 
may  be  at  once  published  by  an  author  at  a  meeting  of  a  scientific 
society,  or  in  a  scientific  journal,  or  in  any  other  way  he  may  desire  ; 
in  that  case,  he  is  expected  to  send  a  short  report  on  the  subject  to 
the  Conference. 

The  annual  meetings  are  usually  held  in  the  provinces,  at  the 
time  and  place  of  the  visit  of  the  British  Association ;  that  for 
1878  will  be  held  in  Dublin  on  Tuesday  and  Wednesday,  the  13th 
and  14th  of  August. 

Gentlemen  desiring  to  join  the  Conference,  can  be  nominated  at 
any  time  on  applying  to  either  of  the  secretaries  or  any  other  officer 
or  member.  The  yearly  subscription  is  seven  shillings  and  sixpence, 
payable  in  advance,  on  July  1st.  Further  information  may  be  ob- 
tained from  the  secretaries — 

Professor  Attpield,  17,  Bloomsbury  Square,  London,  W.C. 
F.  Baden  Benger,  F.C.S.,  7,  Exchange  Street,  Manchester. 


THE  YEAR-BOOK  OF  PHARMACY. 

The  Conference  annually  presents  to  members  a  volume  of  500  to 
GOO  pages,  containing  the  proceedings  at  the  yearly  meeting,  and  an 
Annual  Report  on  the  Progress  of  Pharmacy,  or  Year-Book,  which 
includes  notices  of  all  pharmaceutical  papers,  new  processes,  prepa- 
rations, and  formulae  published  throughout  the  world.  The  neces- 
sary funds  for  accomplishing  this  object  consist  solely  of  the  sub- 
scriptions of  members.  The  Executive  Committee,  therefore,  call 
on  every  pharmacist — principal,  assistant,  or  pupil — to  offer  his 
name  for  election,  and  on  every  member  to  make  an  effort  to  obtain 
more  members.  The  pi'ice  of  the  Year-Book  to  non-members  is 
ten  shillings.  The  constitution  and  rules  of  the  Conference,  and  a 
convenient  form  of  nomination,  will  be  found  at  page  345. 


LIST  OF  CONTENTS. 


PAGK 

Introduction 1 

Pharmaceutical  Chemistry    ..........  19 

Materia  Medica     ............  155 

Pharmacy 235 

Notes  and  Formulas 289 

Constitution  and  Rules  of  the  British  Pharmaceutical  Conference  .         .         .  345 

Honorary  Members  of, the  Conference 346 

Members  residing  Abroad      ..........  347 

Alphabetical  List  of  Members  of  the  British  Pharmaceutical  Conference        .  350 

,,                 „      Towns  at  which  Members  reside     .....  391 

Associations  inyited  to  send  Delegates  to  the  Annual  Meeting        .         .         .  413 

Presentation  Copies  of  the  Tear-Book,  to  whom  forwarded    ....  414 

List  of  Journals  received  in  Exchange  for  the  Year-Book  of  Pharmacy  •         .  415 

Transactions  of  the  British  Pharmaceutical  Conference          ....  417 

General  Index 639 


INTRODUCTIOX 


The  record  of  pharmaceutical  research  forms  an  important  if  but 
a  small  part  of  the  scientific  literature  of  the  year.  A  period  of 
bustling  activity,  embracing  as  it  does  the  numerous  and  not  wholly 
unsensational  reports  on  jaborandi  and  salicylic  acid,  has  been  fol- 
lowed by  an  interval  of  compai-atively  quiet  but  none  the  less 
valuable  research.  Many  new  observations  full  of  interest  to  phar- 
macists have  been  made,  older  ones  have  been  confirmed,  others 
disproved,  and  fresh  light  has  been  shed  on  subjects  which  hitherto 
appeared  in  an  almost  hopeless  state  of  confusion.  As  a  striking 
instance  in  which  skill  and  perseverance  combined  have  raised  an 
important  subject  of  investigation  from  a  condition  little  better 
than  chaos  to  a  fruitful  field  of  inquiry,  we  refer  to  the  chemistry  of 
aconite  root,  as  elucidated  by  successive  annual  contributions  to  the 
British  Pharmaceutical  Conference,  and  especially  by  the  reports  pre- 
sented to  its  recent  meeting  at  Plymouth  by  Dr.  Wright,  Mr.  Groves, 
Mr.  Williams,  Dr.  Paul  and  Mr.  Kingzett.  The  three  chemists  first 
named  constitute  a  committee  specially  appointed  at  the  previous 
meeting  to  continue  investigations  on  the  aconite  bases.  From 
these  and  former  reports  it  appears  that  the  roots  of  Aconitum  Na- 
pellus  contain  three  distinct  alkaloids,  viz.  aconitine,  Cs^H^sN^O^O' 
a  highly  active  crystallizable  body,  furnishing  erystallizable  salts; 
pseudaconitine,  CggH^gNOji,  likewise  active  and  crystallizable,  but 
not  readily  yielding  crystallized  combinations ;  and  an  amorphous 
base  with  a  higher  percentage  of  carbon,  yielding  non-crystalline 
salts,  and  possessing  little  physiological  potency.  The  amorphous, 
bitter,  inert  alkaloid,  furnishing  well  crystallized  salts  and  answering 
to  the  formula  Cg^  H^-  N  O^o,  which  Mr.  Groves  isolated  from  one 
batch  of  roots  (see  Year-Booh  of  Pharmacy,  1875,  p.  514),  is  now 
distinguished  from  the  other  bases  by  the  name  picraconitine.  Th^ 
roots  of  Aconitum  fevox  are  shown  to  contain  comparatively  large 
quantities  of  pseudaconitine,  besides  a  small  amount  of  aconitine 
and  an  amorphous  base  with  a  larger  percentage  of  carbon,  which, 
however,  does  not  appear  to  be  identical  with  the  analogous  body 
from  Acordiura  Xapellus. 

The  results  of  Messrs.  Paul  and  Kingzett's  researches  on  Japanese 

3 


2  INTRODUCTION. 

aconite  point  to  the  existence  therein  of  a  crjstalHzable  alkaloid  of 
the  formula  CigHjgN  O9,  differing  from  any  of  the  bases  described 
by  other  observers.  In  Dr.  Wright's  opinion  this  substance  is  not  a 
distinct  alkaloid,  but  a  mixture  of  pseudaconitine  and  decomposition 
products  thereof;  but  tliis  view  is  stoutly  contested  by  the  two- 
authors  just  named.  The  latter,  on  the  other  hand,  incline  to  the 
belief  that  the  various  bodies  which  have  been  described  as  aconite 
bases  may  be  combinations  of  alkaloids  with  aconitic  or  some  other 
organic  acid  ;  and  that  it  is  doubtful  whether  the  alljaloid  or  alka- 
loids to  which  the  medicinal  properties  of  aconite  are  ascribed  have 
ever  yet  been  obtained  in  a  separate  state.  That  some  diversity  of 
opinion  should  still  continue  to  exist  on  this  subject  appears  the 
less  surprising  in  view  of  the  great  difficulties  connected  with  its 
investigation,  arising  mainly  from  the  great  tendency  of  these 
alkaloids  to  undergo  changes  during  their  extraction  and  puriScation. 
The  nature  of  these  changes,  so  readily  brought  about  under  various 
influences,  form  one  of  the  leading  features  of  the  Committee's 
report  already  referred  to,  and  is  briefly  represented  by  the  follow- 
ing equations  : — 

(1)  CasH^oNO,.   -1-    H.O   =    C;H,,0,    +   C.gHcgNOn 

Aconitine.  Benzoic  ncid.  Aconinc. 

(2)  C36H,9XOn   +   11,0   =   CoHioO,   +   a^^H^iNOs 

Pseud-  Dimetbylproto-  Pseud- 

aconitine catechuic  acid.  aconine. 

These  decomposition  products  never  fail  to  be  present  in  the 
extract  prepared  from  aconite  roots,  and  in  the  aconitine  of  com- 
merce. The  latter  appears  to  be  a  mixture  of  true  aconitine  and 
pseudaconitine,  with  variable  quantities  of  aconine  and  pseud- 
aconine,  and  of  the  amorphous  unnamed  alkaloids  above  alluded 
to.  A  process  for  its  analy.sis  will  be  found  on  page  4G4  of  this 
volume,  as  part  of  the  report. 

Prof.  DragendorfTs  statement  that  Tanret's  ergotinine  was  not  a 
chemically  distinct  substance,  but  a  mixture  owing  its  activity  to 
the  presence  of  sclererythrin,  is  conti-adicted  by  ]\I.  Tanret,  who 
supplies  analytical  evidence  to  show  that  his  alkaloid  does  not 
contain  even  a  trace  of  this  body.  Sclerotic  acid,  claimed  to  be  the 
active  principle  of  ergot,  is  dealt  with  by  its  discoverers,  Prof. 
Dragondorff  and  M.  Podwissotzky,  in  a  second  report  containing 
detailed  information  respecting  the  process  employed  for  its  extrac- 
tion. Prof.  Buchheim,  on  the  other  hand,  is  still  of  opinion  that  no- 
alkaloid   or  glucoside  fully  representing  the  active    properties    Ou 


INTRODUCTION.  t> 

ero-ot  has  as  yet  been,  or  is  ever  likely  to  be,  isolated  from  the  drug, 
nnd  that  the  freshly  prepared  extract  alone  can  be  depended  upon 
for  medicinal  purposes. 

There  can  be  no  longer  any  reasonable  doubt  that  the  reported 
conversion  of  brucine  into  strychnine  by  the  action  of  dilute  nitric 
acid  was  an  illusion ;  for  as  such  it  must  appear  in  the  absence  of 
evidence  to  the  contrary  from  the  results  of  experiments  on  this 
subject  conducted  by  Mr.  A.  J.  Cownley,  and  more  recently  by  Mr. 
W.  A.  Shenstone.  In  both  reports  attention  is  drawn  to  the  facility 
with  which  traces  of  strychnine  and  brucine  are  destroyed  by  dilute 
nitric  acid,  an  important  point  in  forensic  investigations.  A  new 
process  for  the  detection  of  these  and  other  poisonous  alkaloids  in 
analyses  of  this  kind  is  recommended  by  Prof.  Dragendorff;  its  chief 
feature  consisting  in  the  application  of  benzol  and  petroleum  ether 
as  solvents. 

Dr.  Paul  criticises  the  official  test  of  the  purity  of  quinine  sul- 
phate, showing  that  it  fails  to  indicate  the  presence  of  less  than  ten 
per  cent,  of  sulphate  of  cinchonidine,  this  failure  being  due  to  an 
increased  solubility  of  cinchonidine  in  ether  in  the  presence  of 
quinine.  He  prefers  to  i-ely  on  the  process  of  fractional  crystalliza- 
tion, whereby  the  cinchonidine  sulphate,  as  the  more  soluble  salt  of 
the  two,  remains  in  the  uaother-liquor,  in  which  it  may  then  be 
readily  detected  by  the  official  test.  In  an  examination  of  nine 
samples  of  commercial  quinine  sulphate,  he  found  cinchonidine  in  all 
cases,  varying  in  amount  from  one  to  ten  per  cent.  Equally  import- 
ant to  pharmacists  is  the  same  author's  observation  that  some  of 
the  citrate  of  iron  and  quinine  sold  as  the  preparation  of  the  British 
Pharmacopoeia  is  lamentably  deficient  in  alkaloid,  and  still  more  so 
in  actual  quinine.  The  amount  of  water  of  crystallization  in  freshly 
prepared  quinine  sulphate  has  been  variously  stated  as  7,  7^,  and  8 
molecules.  According  to  a  recent  determination  by  Mr.  Cownley,  it 
amounts  to  7^  molecules,  of  which  5  molecules  are  rapidly  lost  by 
efflorescence;  the  salt  becomes  anhydrous  at  100°  C,  but  re-absorbs 
2  molecules  of  water  upon  exposure  to  the  air.  Aricine,  it  seems, 
must  be  erased  from  the  list  of  cinchona  alkaloids,  since  Dr.  0. 
Hesse's  examination  of  this  substance  and  the  so-called  cinchovatinc 
affijrds  the  strongest  ground  for  regarding  both  as  impure  cinchoni- 
dine. 

The  alteration  which  acetate  of  mor})hinc  is  known  to  undergo  on 
keeping  is  attributed  by  ]\Ir.  E.  Merck  to  a  continual  thoixgh  slow 
elimination  of  acetic  acid,  resulting  in  the  formation  of  a  basic  salt 
less  soluble  in  water  but  unimpaired  in  its  active  properties.      So 


-*•  INTRODUCTION. 

long  US  the  preparation  does  not  assume  a  very  distinct  yellow- 
coloration,  indicating  a  further  and  more  complicated  decomposition, 
it  remains  fit  for  medicinal  use.  Analyses  of  veratrine  performed 
by  ^lessrs.  E.  Schmidt  and  R.  Koppen  show  that  the  composition 
of  the  crystallized  alkaloid  in  its  purest  form  is  represented  by  the 
formula  C^.,  H.,-  N  O9,  and  that  the  commercial  preparation  is  toler- 
ably pure.  Of  the  various  salts  of  conine,  the  hydrobromate  is  the 
one  most  easily  obtainable  in  a  crystallized  state.  A  convenient 
mode  of  preparation,  together  with  a  description  of  its  properties, 
and  suggestions  respecting  its  medicinal  application,  form  the 
subject  of  a  paper  by  ]M.  Mourrut.  The  results  of  an  analysis  of 
the  platinum  salt  of  pilocarpine  have  convinced  Mr.  Kingzett  of  the 
identity  of  this  alkaloid  with  that  to  which  he  has  previously 
assigned  the  formula  Cog  Ho^  X^  0^. 

Dr.  Schmidt's  researches  on  the  aloin  of  Barhadoes  aloes  confirm 
the  correctness  of  the  formula  Cjq  Hjg  Orr  previously  established  by 
Dr.  Tilden,  and  show  that  this  aloin,  like  that  of  Zanzibar  aloes,  may 
ciTstallize  with  either  one,  two,  or  three  molecules  of  water.  Re- 
garding the  oxidation  products  of  barbaloin  and  socaloin.  Dr.  Tilden 
reports  that,  whereas  the  action  of  nitric  acid  on  these  substances 
yields  chrysammic  acid,  their  treatment  with  bichromate  results 
in  the  formation  of  a  peculiar  yellow  compound  of  the  formula 
Cj^HigOg,  named  by  him  aloxantJiin.  When  heated  with  zinc 
dust  this  body  fui-nishes  methylanthracene,  the  same  product  as 
obtained  by  Messrs.  Graebe  and  Liebermann,  and  subsequently  by 
Dr.  Schmidt,  in  the  same  way  direct  from  aloin.  As  a  point  of  special 
interest.  Dr.  Tilden  calls  attention  to  the  relation  between  aloxanthin 
and  the  two  yellow  constituents  of  rhubarb,  chrysophanic  acid  and 
emodin,  as  becoming  evident  ou  comparison  of  their  f ormulije : — 

(CH., 
Chrysophanic  Acid,  Cy  Hi,j  0.^-  C^H-  •'  (O  H).-, 

Emodin.     .     .     .     Ci5Hi,0,--.Ci,H,J  (0H)3 

(Oo 

rcH, 

Aloxanthin     .     .     Cj^  B^^^  0^  -  Cj^  H3  <  (0  H)^ 

io, 

from  which  the.se  cumpounds  appear  as  di-,  tri-,  and  tetra-oxyderi- 
vatives  of  methylanthraquinone. 


INTKODUCTION'.  O 

Amyriii,  tlie  principal  constituent  of  olemi,  has  been  I'O investigated 
by  Dr.  E.  Buri,  who  gives  the  formula  G,-^  H^o  0,  or  (G-  Hy);  H.O, 
as  the  proper  representation  of  its  composition.  According  to  Prof. 
Fliickiger  it  is  associated  in  elemi  with  icacin,  (C5  Hg)g  H^  0, 
bryoidin,  (Cg  Hg)^^  Ho  0,  and  a  volatile  oil,  (C-  H^),.  Dr.  Buri's 
analysis  of  capsaicin,  the  pungent  principle  isolated  from  capsicum 
fruit  by  Mr.  Thresh,  leads  to  the  formula  Cg  H^^  Oo,  the  correctness 
of  which  is  now  confirmed  by  Mr.  Thresh's  own  determinations. 
Kosin,  a  crystalline  body  prepared  by  Dr.  Merck,  and  described  by 
Professor  Fliickiger  (see  Year-Booh  of  Pharmacy,  1875,  p.  19),  is 
now  asserted  by  Professor  Buchheim  to  be,  not  merely  a  definite 
chemical  constituent  of  cusso,  but  also  its  real  active  principle,  and 
as  such  it  is  recommended  by  him  to  the  notice  of  the  medical 
profession. 

Artificially  jDrepared  oil  of  mtistard  is  generally  regarded  as 
identical  with  the  natural  product,  and  so  it  unquestionably  would 
be  if  it  were  prepared  from  allyl  iodide  and  potassium  sulphocyanide  ; 
but  as  such  a  preparation  would  be  more  costly  than  the  oil  obtained 
from  black  mustard  seeds,  the  artificial  oil  of  commerce  is  probably 
the  unpurified  product  of  the  dry  distillation  of  a  mixture  of 
potassium  allyl-sulphate  and  sulphocyanide,  and  as  such  it  is  hardly 
fit  for  therapeutic  purposes.  Dr.  E.  Mylius,  who  reports  on  this 
subject,  finds  that  the  best  artificial  oil  met  with  in  German  com- 
merce contains  about  eight  per  cent,  of  impurities.  In  a  valuable 
contribution  to  the  chemistry  of  essential  oils  presented  to  the 
British  Pharmaceutical  Conference,  Dr.  Tilden  records  the  results  of 
a  further  study  of  the  action  of  nitroxyl  chloride  (N  0  CI)  on 
various  terpenes  of  the  formula  C^,  H^g.  The  results  of  this  re- 
action enable  him  not  only  to  distinguish  true  terpenes  from  the 
polymeric  hydrocarbons  of  the  formulae  C^jH,^,  Cgo  Hgo,  etc.,  but 
also  to  distinguish  between  various  true  terpenes  obtained  from 
different  sources.  He  ari'ives  at  the  conclusion  that  the  terpenes 
from  several  diff'erent  plants  are  really  indentical  and  not  simply 
isomeric.  This  he  believes  to  be  the  case  with  the  terpenes  fi^om 
French  turpentine,  juniper,  and  sage ;  also  with  those  from  orange 
peel,  bergamot,  and  lemon.  Thus  he  divides  the  natural  terpenes 
into  two  groups,  viz.,  the  turpentine  group  and  the  orange  group, 
differing  from  each  other  by  their  boiling  point,  the  melting  points 
of  their  nitroso- derivatives,  and  other  features.  The  difference  in 
odour  which  the  members  of  either  group  exhibit  is  attributed  by 
him  to  the  presence  of  small  quantities  of  the  heavier  constituents 
of  the  oils,  which  it  is  almost  impossible  to  separate  completely  by 


1)  INTRODUCTION. 

distillation.  The  oils  of  lavender  and  savin  do  not  appear  to  be 
terpenes,  as  even  their  most  volatile  fractions  contain  oxygen.  The 
oils  of  caraway  and  sage,  however,  contain  terpenes  besides  oxygen 
compounds.  The  latter  forms  the  subject  of  an  elaborate  report  by 
Messrs.  ^I.  ^I.  Pattison  Muir  and  S.  Sugiura,  which  was  also  read 
at  the  Plymouth  meeting  of  the  Conference.  A  reinvestigation  of 
the  stearoptcn  of  oil  of  cubebs,  by  Dr.  E.  Schmidt,  confirms  the 
correctness  of  the  formula  C^-  Hoj^.  Ho  0,  which  had  been  called  in 
question  by  Messrs.  J.  Jobst  and  0.  Hesse. 

!Mr.  E.  F.  Teschemacher  recommends  a  process  for  the  assay  of 
opium,  the  main  points  of  which  consist  in  the  avoidance  of  the 
use  of  alcohol  for  extracting  the  morphine,  and  the  separation  of 
the  meconic  acid  at  an  early  stage,  thus  preventing  the  formation  of 
a  basic  meconate  on  px'ecipitation  of  the  morphine.  The  same  sub- 
ject is  treated  in  a  supplementary  note  to  his  previous  report  by 
Mr.  B.  S.  Proctor,  in  which  he  suggests  some  further  improvements 
respecting  the  exhaustion  of  opium  by  percolation. 

The  manufacture  of  sodium  carbonate  from  common  salt  by  the 
so-called  ammonia  process  is  already  undergoing  important  modifi- 
cations. Hitherto,  the  main  step  in  the  process  was  the  formation 
of  sodium  bicarbonate  (see  Year-Boole  of  Pharmacy ,  1874,  p.  171). 
The  improvement  now  introduced  is  based  upon  the  comparative 
insolubility  of  monohydrated  sodium  carbonate  (Na^  C  O3.  Hn  0)  in 
a  concentrated  solution  of  sodium  chloride.  This  carbonate  crystal- 
lizes at  60°-70°  C.  from  a  mixed  saturated  solution  of  ammoniura 
carbonate  and  common  salt  containing  the  latter  in  excess.  It  is 
converted  into  the  ordinary  carbonate,  Xa^  C  O3. 10  Ho  0,  by  simple 
recrystallization. 

The  question,  whether  two  different  salts,  when  dissolved  together 
in  water,  exist  in  the  solution  in  the  same  condition  in  which  they 
were  introduced,  or  whether  they  suffer  a  mutual  decomposition,  is 
difficult  to  decide  in  cases  in  which  such  a  decomposition  does  not 
result  in  the  foi-mation  of  an  insoluble  or  difficultly  soluble  combina- 
tion. Some  light  is  thrown  on  this  subject  by  Dr.  H.  C.  Dibbits, 
who  bases  his  conclusions  on  the  different  quantities  of  ammonia  lost 
by  solutions  of  different  ammonium  salts  upon  boiling.  By  dissolv- 
ing equivalent  proportions  of  ammonium  sulphate  and  potassium 
chloride,  and  determining  the  loss  of  ammonia  on  boiling,  so  as  to 
ascertain  whether  this  loss  is  equal  to  that  ocurring  with  ammonium 
sulphate,  or  to  that  ocurring  with  ammonium  chloride,  he  finds  the 
boiled  solution  to  contain  ammonium  chloride,  ammonium  sulphate, 
potassium  chloride,  and  potassium  sulphate.     With  other  salts  of 


INTRODUCTION.  / 

potassium  and  ammonium,  the  results  are  the  same,  proving  in  each 
case  a  partial  decomposition  of  the  salts  employed. 

The  chemical  constitution  of  chlorinated  lime  seems  to  afford  an 
unlimited  scope  for  the  exercise  of  chemical  ingenuity,  for  year  after 
year  brings  fresh  contributions  to  its  literature.  The  most  recent  re- 
port on  this  subject  is  one  by  Mr.  C.  Stahlschmidt,  in  whose  opinion 
bleaching  powder  contains  no  free  calcium  hydrate  whatever, 
but  has  a  composition  represented  by  the  formula  2  Ca  H  CI  Oo  + 
Ca  Clo  +  2  Ho  0,   its  main  constituent  being   a  calcium  hydro-oxy- 

chloride,  CaH  CI  0^,  or  Ca<^-.  p,,  which  he  believes  to  be  formed 

by  the  replacement  of  an  atom  of  hydrogen  in  calcium  hydrate 
by  an  atom  of  chlorine.  The  calcium  chloride  he  regards  as  stand- 
ing outside  the  constitution  of  chlorinated  lime. 

Turning  now  to  that  branch  of  chemical  literature  more 
particularly  devoted  to  the  methods  of  analysis,  we  have  again  to 
record  a  number  of  processes  more  or  less  directly  valuable  to 
pharmacists.  Mr.  J\I.  M.  Pattison  Muir  estimates  bismuth  volu- 
metrically,  by  adding  a  titrated  solution  of  potassium  dichromate 
to  a  nearly  neutral  solution  of  bismuth  nitrate  until  the  whole  of 
the  metal  is  precipitated  as  chromate.  The  final  point  of  the  reaction 
is  determined  by  bringing  a  drop  of  the  supernatant  liquid  into  con- 
tact with  a  drop  of  solution  of  silver  nitrate,  when  the  slightest 
excess  of  the  test  will  be  indicated  by  the  formation  of  red  silver 
chromate.  The  titration  of  nitric  acid  by  indigo  requires  certain 
precautious  and  conditions,  the  details  of  which  form  the  subject  of 
;i  paper  by  Mr.  R.  Warington.  Professor  F.  Stolba  has  rendered 
good  service  to  analysts  by  showing  that  the  estimation  of  phos- 
phoric acid  and  magnesium  by  precipitation  as  ammonio  magnesium 
phosphate,  etc.,  may  be  effected  volumetrically.  Instead  of  igniting 
the  washed  precipitate  and  weighing  it  as  pyrophosphate,  it  is  only 
necessary  to  determine  its  alkalinity  by  means  of  deci-normal  hydro- 
chloric acid,  using  cochineal  as  an  indicator.  Arsenic  acid  may  be 
estimated  in  the  same  manner.  The  action  of  the  acid  on  the  pre- 
cipitate is  explained  by  the  following  equation  : — 

Mg.  N  Hj.  P  0^  +  2  H  CI  =  N  H^.  H...  P  0^  +  Mg  CU  ■ 
Mg.  N  H^.  As  0^  +  2  H  CI  =  :^^  H^.  Ho"  As  O^  +  Mg  clg. 

If  magnesium  is  to  be  estimated  in  the  presence  of  calcium,  the 
latter  need  only  be  precipitated  by  ammonium  oxalate  in  the  presence 
of  ammonium  chloride,  and  the  magnesium  then  thrown  down  by 
sodium  phosphate  and  ammonium  hydrate,  without  removing   the 


8  INTEODDCTION. 

calcium  oxalate  by  filtration,  for  the  oxalate  does  not  interfere  in  tlie 
least  with  the  titration  of  the  magnesium  precipitate.  We  have 
had  occasion  to  try  his  process  and  are  much  pleased  with  the 
results.  It  is  evident  that  the  officinal  sodium  phosphate,  Na,.  H.  P  0^, 
may  thus  be  directly  titrated  -without  being  first  converted  into 
ammonio  magnesium  phosphate  : — 

Na..  H.  P.Oj  +  H  CI  -  Na.  H..  P  0^  +  Ka  Cl ; 

or  after  ignition  : — 

Na^.  P.  0;  +  H.  0  +  2  H  Cl  -  2  Na  Ho  P  0^  +  2  Na  Cl. 

Mr.  H.  Pellet  points  out  that  chlorides  can  be  readily  titrated  in 
the  presence  of  phosphates  by  acidifying  the  solution  with  nitric 
acid,  then  neutralizing  with  calcium  carbonate,  and  afterwards  de- 
termining the  chlorine  by  means  of  standard  silver  nitrate  and 
potassium  chromate  in  the  usual  manner.  The  same  chemist,  in 
conjunction  with  M.  F.  Jean,  suggests  the  application  of  baryta 
water  and  a  titrated  acid  for  the  volumetric  estimation  of  oxalates. 
Tannin  is  recommended  by  !Mr.  H.  Kiimmerer  as  a  reagent  in  water 
analysis  on  account  of  its  power  of  precipitating  gelatinous  and 
albuminoid  matters.  A  handy  process  for  estimating  magnesia  in 
potable  waters  is  proposed  by  Mr.  L.  Legler,  and  consists  mainly 
in  the  precipitation  of  the  magnesium  as  hydrate  by  a  known 
quantity  of  sodium  or  potassium  hydrate,  and  the  titration  of  the 
excess  of  alkali  by  standard  sulphuric  acid.  In  estimating  potas- 
sium and  sodium  in  a  mixture  of  their  carbonates  by  the  so-called 
indirect  method,  it  was  hitherto  the  rule  first  to  convert  the  carbon- 
ates into  chlorides  or  sulphates.  This  Dr.  Wittstein  shows  to  be 
unnecessary,  as  the  relative  proportions  of  the  two  carbonates  may 
be  equally  well  calculated  from  the  quantity  of  carbonic  acid  the 
mixture  is  found  to  contain.  Mr.  W.  F.  Koppeschaar  bases  a  volu- 
metric process  for  the  estimation  of  phenol  on  its  well-known  re- 
action with  bromine  water.  The  latter  is  added  in  excess  to  ensure 
complete  precipitation  of  the  phenol  as  Cg  Ho  Brg  0  H,  and  the 
excess  of  the  reagent  determined  by  potassium  iodide  and  standard 
solution  of  sodium  hyposulphide.  The  separation  and  detection  of 
arsenic  in  forensic  analyses  is  best  effected,  according  to  ^Mr.  J.  A. 
Kaiser,  by  heating  the  suspected  organic  matter  with  sulphuric  acid 
and  sodium  chloride,  and  converting  the  chloride  of  arsenic  now 
contained  in  the  distillate  into  arsenic  acid  by  means  of  potassium 
chlorate.  The  product  is  then  in  a  suitable  condition  for  examin- 
ation by  ]Mar.-^h's  test  or  any  of  the  usual  methods.     For  the  quanti- 


INTKODUCTIOX.  \f 

tative  defcerminatiou  of  traces  of  this  poison  in  mineral  and  organic 
substances,  M.  Crommydes  strongly  recommends  Gautior's  process, 
which  consists  in  the  evolution  of  the  ai'sonic  from  a  i\Iarsh's  appa- 
ratus in  the  form  of  arseniuretted  hydrogen,  and  the  direct  weighing 
of  the  metallic  arsenic  deposited  in  the  combustion  tube.  On  theo- 
retical grounds  we  cannot  but  doubt  the  accuracy  of  this  method, 
for  it  is  well  known  that  an  appreciable  portion  of  the  arsenic  in- 
troduced into  Marsh's  apparatus  remains  in  it  as  such  with  the 
zinc.  The  results  of  M.  Crommydes'  experiments,  however,  exhibit 
nevertheless  a  high  degree  of  accuracy,  and  such  being  the  case,  we 
beg  to  recommend  this  apparently  very  handy  and  expeditious  pro- 
cess to  the  further  notice  of  critical  investigators. 

The  analysis  of  food  and  drugs,  or  rather  the  detection  of  adulter- 
ation therein,  is  a  subject  which  during  the  last  six  years  has  re- 
ceived so  many  contributions  that  it  may  almost  be  said  to  have  a 
literature  of  its  own.  This  is  no  doubt  a  direct  consequence  and,  we 
venture  to  say,  one  of  the  best  results  of  the  Adulteration  Act,  a 
result  which,  we  trust,  may  long  continue  to  accrue  from  its  operation. 
During  the  current  year  the  published  researches  bearing  on  this 
subject  have  been  fewer  in  number  than  heretofore,  but  this  is  pro- 
bably to  be  regarded  merely  as  a  temporary  lull  to  be  followed  by 
an  increased  activity.  One  of  the  most  difficult  tasks  a  public 
analyst  may  be  called  upon  to  perform,  and  one  which  but  a  few 
years  ago  would  have  been  wholly  beyond  his  power,  is  the  detection 
and  estimation  of  admixtures  of  foreign  fats  in  butter.  Even  now 
the  processes  employed  for  this  purpose  can  hardly  be  said  to  be 
entirely  satisfactory,  but  they  have  unquestionably  been  much 
advanced  by  the  researches  of  Messrs.  Angell  and  Hehner,  and  more 
recently  by  the  reports  of  Dr.  Muter  and  Dr.  Dupre,  from  which  it 
appears  that  the  specific  gravity  of  the  butter  fat,  together  with  its 
percentages  of  soluble  and  insoluble  fatty  acids,  afford  a  fairly  reli- 
able indication  of  the  presence  or  absence  of  adulteration.  An 
excellent  and  withal  very  simple  mode  of  detecting  mineral  acids 
in  vinegar  is  recommended  by  Mr.  Hehner,  who  relies  for  this  pur- 
pose on  the  reaction  of  the  ash.  The  traces  of  alkaline  acetates  and 
tartrates  invariably  occurring  in  vinegar  are  converted  into  car- 
bonates by  incineration,  and  thus  impart  an  alkaline  reaction  to 
the  ash.  An  admixture  of  sulphuric  or  hydrochloric  acid  would 
convert  these  acetates  and  tartrates  into  sulphates  or  chlorides ; 
thus  causing  the  ash  of  such  vinegar  to  be  neutral  to  test  paper. 
The  quantity  of  the  adulterant  is  ascertained  by  mixing  the  vinegar 
with  a  measured  volume  of  deci-normal  solution  of  soda,  evaporating 


1 0  INTRODUCTION. 

the  mixture  to  dryness,  incinerating  the  residue,  and  determining 
the  loss  of  alkalinity  by  titration  with  deci-normal  sulphuric  acid. 
This  process  is  likewise  applicable  for  the  estimation  of  mineral 
acids  in  adulterated  lime  or  lemon  jnice.  Sulphuric  acid  may  also 
be  detected  in  vinegar  by  means  of  a  reaction  of  colchicine  described 
by  Prof.  Fliickiger.  The  same  chemist  reports  on  the  characters  of 
gurjun  oil,  and  its  detection  in  copaiba  by  means  of  carbon  bisul- 
phide and  a  mixture  of  sulphuric  and  nitric  acids.  For  the  deter- 
mination of  fatty  oils  in  adulterated  copaiba,  Dr.  Muter  makes  use  of 
a  process  based  on  the  different  degrees  of  solubility  of  the  sodium 
salts  of  oleic  and  copaivic  acids  in  a  mixture  of  ether  and  alcohol. 
Mr.  Greenish  supplies  pharmacists  with  some  further  valuable 
information  concerning  the  use  of  the  microscope  for  the  detection 
of  adulteration,  by  drawing  attention  to  the  distinctive  character  of 
cassava  starch,  the  pi'oduce  of  ManiJwt  utlUsstma,  which  has  been 
repeatedly  observed  as  an  adulterant  of  arrowroot.  The  same 
instrument  is  shown  by  j\lr.  W.  J.  Clark  to  afford  a  ready  means 
for  the  recognition  of  an  admixture  of  seed  or  rind  with  the  pow- 
dered pulp  of  colocynth.  An  unusual  amount  of  attention  has  been 
devoted  to  the  testing  of  wines,  and  the  detection  therein  of  fuchsine 
and  other  artificial  colouring  matters.  Abstracts  of  the  most  im- 
portant papers  bearing  on  this  subject  will  be  found  in  this  volume. 
The  influence  of  desiccation  and  other  modes  of  preservation  of 
various  vegetable  articles  of  food  forms  the  subject  of  a  chemical 
study  by  Prof.  Attfield,  the  results  of  which  are  embodied  in  an 
interesting  report  read  at  the  Plymouth  meeting  of  the  British 
Pharmaceutical  Conference. 

The  question  whether  or  not  copper  is  to  be  considered  a  poison 
has  been  much  discussed  of  late,  without  leading  to  anything  like 
unanimity  of  opinion.  It  appeal's  to  be  generally  conceded,  how- 
ever, that  this  metal  is  not  a  poison  in  the  same  sense  in  which 
arsenic,  lead,  and  mercury  are  termed  poisons ;  it  does  not  directly 
produce  fatal  effects,  and  workmen  engaged  in  its  production  and  in 
the  manufacture  of  its  salts  do  not  seem  to  suffer  in  health  from 
their  occupation.  Messrs.  Paul  and  Kingzett  believe  that  preserved 
peas  coloured  with  small  quantities  of  copper  salts,  such  as  those 
largely  imported  from  France,  are  pei-fectly  harmless,  basing  their 
opinion  on  the  observation  that  the  greater  part  of  this  metal  thus 
introduced  into  the  stomach  is  eliminated  Avith  the  fajccs.  All  that 
is  positively  known  respecting  the  action  of  copper,  is  that  in  large 
or  even  in  moderate  doses  it  produces  vomiting  and  other  violent 
symptoms,  and  that  in  smaller  doses  it  produces  asti-ingent  effects ; 


INTKODUCTION.  1 J 

but  Avhether  the  regular  and  long  continued  introduction  of  minute 
quantities,  such  as  occur  in  coloured  vegetables,  may  or  may  not  be 
detrimental  to  health,  is  at  preset,  we  think,  an  open  question,  the 
final  solution  of  which  lies  outside  the  sphere  of  chemical  research. 

MM.  Dujardin  Beaumetz  and  Audige  have  studied  the  effects 
on  dogs  of  liyjiodermic  injections  of  glycerin,  and  arrive  at  the  con- 
clusion that,  when  administered  in  large  doses,  this  substance 
possesses  decided  toxic  properties,  producing  symptoms  analogous 
to  those  of  acute  alcoholism.  This  fact,  apart  from  its  thei-apeutic 
value,  cannot  fail  to  be  interesting  to  chemists  who  regard  glycerin 
as  an  alcohol  of  the  formula  Cg  Hj  3  H  O. 

Among  the  vegetable  drugs  which  during  the  present  year  have 
formed  the  objects  of  chemical  and  medical  research,  there  are  not 
many  that  can  be  classed  as  new  remedies,  the  majority  of  them 
having  met  with  previous  notices.  Xanthinm  spinosimi  is  introduced 
as  a  remedy  for  hydrophobia,  and  strongly  recommended  as  such  by 
Dr.  Grzymala.  M.  Guichard,  who  deals  with  the  chemistry  and 
pharmacy  of  this  drug,  considers  an  alcoholic  extract  as  the  best 
form  for  its  administration,  and  states  that  he  has  obtained  indica- 
tions therein  of  the  presence  of  an  alkaloid  which  he  soon  hopes  to 
isolate.  Olive-tree  bark  is  spoken  of  as  a  valuable  febrifuge,  owing 
its  therapeutic  properties  to  a  principle  similar  in  its  action  to 
quinine,  to  which  the  name  oliverine  has  been  given.  The  same 
properties  are  attributed  to  the  so-called  quinine  flower,  a  drug 
derived  from  a  gentianaceous  plant  growing  in  Florida.  The  root 
of  Smvi  latifolium,  a  Californian  plant  belonging  to  the  order 
Umhelliferce,  is  reported  to  possess  toxic  properties,  resembling 
those  of  digitalis  and  due  to  a  resinous  constituent.  Mate,  or  Para- 
guayan tea,  is  said  to  be  obtained  from  the  leaves  and  young 
branches  of  Hex  mate  paraguayensis,  and  to  contain  a  considerable 
amount  of  caffeine ;  its  prolonged  use  as  a  beverage  appears  to  prove 
injurious  to  the  heart  and  digestive  organs.  The  root  of  Mer/arrhiza 
Californica  is  described  as  a  strong  di'astic  and  hydragogue  purga- 
tive, owing  its  action  to  a  glucoside  named  megarrhizin,  which 
agrees  in  many  of  its  chemical  and  physical  properties  with  colo- 
cynthin  and  bryonin,  but  is  not  identical  with  either.  The  alcoholic 
extract  of  the  root  may  be  administered  in  doses  varying  from  an 
eighth  of  a  grain  to  half  a  grain,  and  will  probably  prove  very 
useful  in  dropsical  conditions,  as  it  also  augments  the  urinary  dis- 
charges ;  in  large  doses  it  is  a  powerful  irritant,  causing  gastro- 
enteritis and  death.  An  alkaloid  named  timbonine  has  been  isolated 
by  M.  Martin  from  the  root  bark  of  timbo  (PaidUnia  2^innaia),  a 


12  INTKODUCTION. 

Bi-azilian  dnig  which  is  used  in  the  form  of  poultices  as  an  irritant. 
Mr.  A.  Kopj)  gives  a  description  of  an  odorous  resin,  called  rcsiiia 
iiuaiaci  jH'riuu'iina  aromatlca,  the  origin  of  which  is  as  yet  unknown. 
It  is  stated  to  be  entirely  different  from  true  guaiacum  resin,  and  to 
yield  ujiou  distiUation  with  v/atcr  a  volatile  oil  the  odour  of  which 
resembles  a  mixture  of  peppermint  and  lemon.  Hoang-Nan  is  the 
name  of  a  bark  which  is  said  to  be  much  esteemed  in  Toug-King 
(in  Eastern  Asia)  as  a  remedy  for  hydrophobia.  Specimens  of  this 
drug  received  and  examined  by  M.  Planchon  correspond  in  every 
])articular  with  the  bark  of  Sfrijchnos  nux  vomica.  The  description 
of  a  large  number  of  Indian  drugs,  their  botanical  sources,  and  the 
uses  to  which  they  are  applied,  forms  the  subject  of  an  interesting 
and  very  extensive  report  by  Prof.  Dymock,  published  in  the  Phar- 
maceutical Society's  Journal. 

^Ir.  J.  Jobst  reports  that  his  attempts  to  prepare  cotoiu  from 
recent  importations  of  cota  bark  have  failed  in  their  immediate 
object,  but  have  led  to  the  isolation,  by  the  same  process  which  pre- 
viously yielded  cotoin  (see  Year-Booh  of  Fharmacy,  1876,  p.  150), 
of  a  body  similar  to  and  possessing  the  same  therapeutic  proper- 
ties as  cotoin.  This  he  proposes  to  call  2^'^^^'<^''(^otoin.  The  bark 
itself  differs  from  that  previously  operated  upon  in  its  external 
appearance  as  well  as  in  its  odour  and  taste.  A  subsequent  examin- 
ation of  the  recently  imported  bark  shows  the  presence  therein  of 
four  distinct  crystalhue  principles,  viz.  paracotoin.  Cjg  Hj^  Og  ;  leu- 
cotin,  Coi  HoQ  Og  ;  oxyleiicotin,  Coj  Hoq  O7  ;  and  hijdrocotoin,  Cno  Hoq  Og. 
Cotoin  is  now  found  to  have  a  composition  corresponding  to  the 
formula  Coo  Hjg  Og,  from  which  paracotoin  appears  to  be  a  homo- 
logue  differing  by  C3  Hg.  The  latter,  notwithstanding  its  high  price, 
is  finding  much  favour  as  a  remedy  against  all  forms  of  diarrhoea. 

MM.  Gallois  and  Hardy  publish  the  details  of  a  chemical 
investigation  of  mancona  bark,  the  produce  of  ErijthrojjJdoeurn 
ffiiiiieoise,  resulting  in  the  isolation  of  a  strongly  poisonous  alkaloid, 
to  which  they  give  the  name  cri/throjJdeine.  It  resembles  strych- 
nine in  its  reaction  with  ])otassium  permanganate  and  sulphuric 
acid,  but  the  coloration  thus  produced  is  less  intense,  and  soon 
changes  to  a  dirty  brown.  The  bark  of  Galipea  Casparia,  commonly 
known  as  angostura  bark,  has  also  furnished  a  new  alkaloid,  which 
Me.s.srs.  Oberlin  and  Schlagdcnhauffen  find  to  be  soluble  in  ether, 
chloroform,  and  benzoline,  and  to  differ  entii-ely  from  Saladin's 
cusparme.  On  the  other  hand,  the  asserted  existence  of  an  alkaloid 
iu  scammony  root  is  dis])uted  by  Messrs.  Kingzett  and  Parries. 
Resin  of  si-ammony,  according  to  the  same  authors,  is  a  glucoside. 


INTRODUCTION.  lo 

differing  but  little  from  jalapin.  The  toxic  properties  of  Persian 
insect  powder  (the  flowers  of  P^retlinoni  caucasicuvi)  also  appear  to  be 
due  to  a  glucoside,  for  such  the  body  named  persicin,  prepared  and 
described  by  Mr.  R.  Rotlier,  proves  to  be. 

The  active  properties  of  Indian  hemp  have  hitherto  been  ascribed 
to  its  resinous  constituents.  Dr.  Preobraschensky,  however,  shows 
that  commercial  hashish,  as  well  as  the  flowering  tops  of  the  plant, 
and  the  pure  extract  prepared  therefrom,  all  contain  a  volatile 
alkaloid  which,  in  odour,  taste,  the  crystalline  forms  of  its  salts, 
and  its  reactions  with  platinic  chloride  and  other  tests,  corresponds 
exactly  with  nicotine.  Two  grams  of  the  extract  distilled  with  lime 
and  potash  furnished  63'5  milligrams  of  nicotine. 

Professor  Buchheim's  research  on  the  constituents  of  black  pepper 
establishes  the  fact  that  the  amorphous  substance  pi-eviously  denoted 
as  "  resin,"  is  a  distinct  principle,  which,  like  piperin,  yields  piperi- 
din  when  treated  with  alcoholic  solution  of  potash.  While  piperin 
may  be  regarded  as  piperidin,  C5  H  -^o  H  I^,  in  which  one  atom  of 
hydrogen  is  replaced  by  pipericacid,  C5  H^q  (C^oHg  O3)  N,  chavicin, 
the  body  referred  to,  is  to  be  considered  as  piperidin  in  which  an 
atom  of  hydrogen  is  replaced  in  a  similar  manner  by  chavicic  acid. 
A  part  of  Mr.  Thi'esh's  report  on  cayenne  pepper  deals  with  the 
fatty  matter  obtained  from  it,  proving  free  palmitic  acid  to  be  its 
predominating  constituent. 

Pumpkin  seeds,  according  to  Mr.  E.  Heckel,  owe  their  anthelmin- 
tic action  to  a  resinous  substance  contained  in  the  outer  layer  of  the 
fourth  or  innermost  coat  of  the  seed,  and  not,  as  was  formerly  sup- 
posed, to  the  fatty  oil  residing  in  the  cotyledons.  Owing  to  the 
absence  of  this  papyraceous  membrane,  which  alone  contains  the 
resin,  in  other  cucurbitaceons  seeds,  the  latter  are  said  to  be  inert. 
At  the  same  time  it  is  shown  that  even  active  seeds  become  inert  by 
being  blanched  in  a  fresh  state,  as  all  the  coats  are  thereby  removed. 
The  seeds  of  Uicinus  communis  form  the  subject  of  an  examination 
by  Mr.  E.  L.Boerner,  showing  them  to  contain,  in  addition  to  the  fatty 
oil,  emulsin,  sugar,  and  a  crystallizable  body  possessing  none  of  the 
characters  of  an  alkaloid. 

In  a  paper  read  before  the  Pharmaceutical  Society,  Mr.  H.  Senier 
supplies  some  interesting  information  respecting  the  nature  of  the 
colouring  matter  contained  in  the  petals  of  Eosa  gallica.  This  sub- 
stance appears  to  be  an  acid  capable  of  forming  well-defined  crystal- 
lized salts  with  the  alkali  metals.  The  numbers  obtained  in  an 
analysis  of  the  lead  salt  lead  to  the  formula  Pb^  Co^  H^g  Oo^. 

Emodin,  one  of   the  constituents  of  rhubarb,  is  now  known  to  be 


li  INTRODUCTION. 

also  a  constituent  oE  the  bark  of  Bhamnus  frangula.  Messrs. 
Liebermaim  and  "Waldstein,  who  have  isolated  this  substance  from 
a  parcel  of  old  bark,  admit  that  it  is  not  quite  identical  with  the 
frangulic  acid,  or  frangulin,  obtained  bj  Faust,  and  consider  it 
probable  that  the  latter  may  exist  in  the  recent  bark  and  become 
gradually  converted  into  emodin  by  oxidation.  Such  a  change,  if 
confirmed,  would  throw  light  on  the  hitherto  unexplained  fact  that 
this  bark  requires  to  be  ke2)t  for  at  least  twelve  months  before  it 
is  suitable  for  medicinal  use  (see  Year-Book  of  Pharmao/,  1876, 
p.  162). 

The  presence  of  tannic  acid  in  gentian  root,  first  asserted  by  Mr. 
E.  L.  Patch,  and  subsequently  disputed  by  Professor  Maisch,  is  now 
confirmed  by  M.  Ville,  who  finds  that  the  colouring  matter  of  gen- 
tian, known  as  gentianin,  gives  unmistakable  reactions  with  ferric 
chloride,  albumen,  and  gelatine.  Gelsemiuic  acid,  one  of  the  prin- 
ciples isolated  from  the  root  of  Gelsemium  scmpervirens  is  proved  by 
Professor  Sonnenschein  to  be  identical  with  sesculin,  a  substance 
contained  in  the  bark  of  the  horse  chestnut.  Benzoic  and  cinnamic 
acids  are  now  stated  to  occur  in  balsam  of  tolu  in  the  free  state  as 
well  as  in  that  of  their  benzylic  ethers. 

Pi'ofessorBentley  draws  attention  to  the  distinguishing  chai'acters 
of  valerian  and  the  rhizome  and  rootlets  of  Vei-atmm  album,  on 
account  of  an  admixture  of  the  latter  he  has  recently  detected  in  a . 
parcel  of  valerian.  In  a  like  manner,  Mr.  Holmes  deals  with  the 
features  of  distinction  between  aconite  root  and  the  root  of  master- 
wort,  Imperatoria  odrutlimm,  which  he  has  observed  to  occur  as  an 
adulterant  or  admixture  in  the  former.  Considering  the  cheapness 
of  aconite  root,  !Mr.  Holmes  attributes  this  adulteration  to  care- 
lessness in  collecting  the  drug,  an  opinion  which  receives  much 
support  from  an  article  on  masterwort  published  in  the  Pharma- 
ceutische  Zeitunrj,  an  abstract  of  which  will  be  found  on  page  '100  of 
this  volume. 

Notwithstanding  all  that  has  been  said  and  written  with  reference 
to  the  syrups  of  phosphates  of  iron,  this  subject  still  continues  to 
engage  attention,  as  may  be  seen  from  the  further  contributions  it 
has  received  during  the  cui-rent  year.  A  ferric  citrophosphate,  of  the 
formula  Fcj.  P  0^.  Cg  Hj  0^,  is  described  and  recommended  by  Mr. 
Rother  as  superior,  both  as  regards  flavour  and  the  stability  of  its 
solution,  to  all  similar  combinations  now  in  use.  Among  the  modern 
ferric  preparations  employed  as  therapeutic  agents,  a  solution  of  a 
very  basic  oxychloride,  known  as  "J'crrum  dialysatum,"  deserves  to 
be  mentioned  here  as  one  rapidly  gaining  favour  with  the  medical 


INTKODUCTION.  15 

profession  on  account  of  its  non-astringenej  and  ready  assimilation 
in  the  system.  Its  history,  mode  of  preparation,  and  properties  form 
the  subject  of  several  papers  contained  in  this  vohime.  The  process 
of  dialysis  will  probably  before  long  find  a  more  extensive  applica- 
tion in  pharmacy  than  has  hitherto  been  the  case  ;  for  not  only  does 
it  afford  an  easy  and  very  simple  means  of  separating  crystallizable 
substances  from  gummy,  extractive,  colouring,  and  other  colloid 
matters,  but  it  may  also  serve,  as  Mr.  Rother  shows,  for  the  concen- 
tration of  solutions  of  crystalloids  without  the  aid  of  heat,  an 
important  point  considering  the  injurious  influence  of  the  latter  on 
many  vegetable  alkaloids  and  other  active  principles. 

The  pharmacy  of  sugar  receives  able  treatment  at  the  hands  of 
Dr.  Symes  in  a  paper  read  before  the  British  Pharmaceutical  Con- 
ference, in  which  he  deals  with  the  various  objects  for  which  sugar 
is  used  in  pharmaceutical  preparations,  the  condition  in  which  it 
should  be  used,  its  inversion  by  acids,  and  other  points  of  interest. 
Mr.  E.  Gregory  criticises  the  various  modes  of  preparing  emulsions, 
and  arrives  at  the  conclusion  that  the  use  of  mucilage  in  these 
processes  should  be  abandoned  in  favour  of  powdered  gum.  For 
the  preparation  of  extracts  known  to  suffer  in  quality  from  the- 
application  of  heat,  Mr.  A.  Herrara  suggests  the  abstraction  of  the 
greater  part  of  the  water  from  the  expressed  juice  or  cold  infusion  by 
repeated  freezing,  and  the  subsequent  evaporation  of  the  mother- 
liquor  at  a  temperature  not  exceeding  oO°  C.  Extract  of  couium 
thus  prepared  has  the  characteristic  odour  of  conine,  and  when 
treated  with  water  yields  a  solution  possessing  the  appearance  and 
all  the  properties  of  the  fresh  juice.  A  cold  process  of  preparing 
essential  oils,  consisting  mainly  in  their  extraction  by  means  of 
petroleum  benzin,  is  described  by  Mr.  L.  Wolff,  who  states  that  oils 
obtained  in  this  manner  have  an  ai'oma  superior  in  many  cases  to 
that  of  the  same  oils  obtained  by  distillation. 

Mr.  B.  Squire  points  out  the  ready  solubility  of  crystallized 
nitrate  of  bismuth  in  glycerin,  and  recommends  such  a  solution 
both  for  internal  and  external  application.  The  chemical  reactions 
of  this  glycerole  induce  jNIr.  J.  Williams  to  regai-d  it  as  a  chemical 
combination,  whereas  Mr.  W.  Willmott,  who  has  likewise  studied  its 
behaviour  with  reagents,  believes  it  to  be  a  mere  solution.  An  obate 
of  bismuth  containing  twenty  per  cent  of  the  oxide  is  suggested  by 
Mr.  S.  C.  Betty  as  a  suitable  external  remedy.  Mr.  Squire  also  pro- 
poses the  use  of  chrysophauic  acid,  one  of  the  principles  of  rhubarb, 
in  the  place  of  goa  powder,  of  which  it  forms  the  chief  constituent. 
It  is  best  applied  in  the  form  of  ointments,  formulse  for  the  prepar- 


1  0  INTKODUCTIUN. 

atiou  of  which  are  given  hotli  by  ~Mr.  Squire  and  Mr.  Gerrard.  Mr. 
W.  W.  Urwick  reports  the  interesting  observation  that  an  albumin- 
atecl  sohition  of  phosphorus  in  a  mixture  of  absolute  alcohol  and 
glycerin  instantly  loses  its  odour  and  taste  on  the  addition  of  a 
few  drops  of  oil  of  neroli,  thus  producing  a  pleasant  and  palatable 
mixture. 

We  cannot,  in  our  opinion,  more  fitly  conclude  this  introductory 
chapter  than  by  drawing  the  attention  of  our  readers  to  Mr. 
Schacht's  account  of  his  experience  in  the  equipment  and  working 
of  a  small  pharmaceutical  laboratory.  His  lucid  description, 
c-oupled  as  it  is  with  excellent  drawings  by  Mr.  J.  Thompson,  will 
serve  as  a  valuable  guide  to  many  a  pharmacist  engaged  in  the 
construction  or  improvement  of  a  laboratory  of  his  own,  and  as  an 
inducement  to  many  others,  who  previously  might  not  have  thought 
of  so  doing,  to  combine  the  work  of  the  laboratory  with  the  duties 
of  the  counter ;  a  combination  which,  if  judiciously  carried  out,  can 
only  result  to  their  advantage.  There  are  among  the  numerous 
preparations  used  in  pharmacy  many,  the  purity  and  strength  of 
which  cannot  be  ascertained  by  reliable  tests ;  and  with  regard  to 
those  the  pharmacist's  best,  if  not  his  only,  safeguard  consists  in  their 
production  by  himself  or  under  his  own  supervision.  Nor  can  the 
education  of  the  modern  student  of  pharmacy  be  deemed  suflficient 
unless  his  knowledge  of  dispensing  and  retail  business  be  supple- 
mented by  a  fair  amount  of  practical  experience  concerning  the 
processes  of  the  pharmacopoeia,  and  this,  it  need  hardly  be  said,  can 
only  be  acquired  in  the  laboratory.  In  many  respects  Mr.  Schacht's 
report  appears  to  us  a  most  valuable  item  in  the  pharmaceutical 
literature  of  the  year,  and  as  such  we  most  heartily  commend  it  ic 
our  readers. 


PHARMACEUTICAL    CHEMISTRY. 


YEAE-BOOK    OF    PHAEMACY. 


PART  I. 

PHARMACEUTICAL    CHEMISTRY. 

The   Detection  of  Arsenic  in  Poisoning  Cases.     J.  A.  Kaiser. 

(Zeitschr.  flir  Aiialijl.-Ckem.,  xiv.,  250-281.)  The  conversion  of  ar- 
senic into  chloride,  and  its  separation  as  such  from  organic  sub- 
stances by  distillation,  is  known  as  one  of  the  best  processes  for  the 
isolation  and  detection  of  tliis  poison  in  forensic  investigations. 
The  author's  method  is  a  modification  of  this  process,  and  consists 
mainly  in  the  conversion  of  the  distilling  chloride  into  arsenic  acid 
by  means  of  fi-ee  chlorine.  The  suspected  Substances  are  introduced 
into  a  large  flaslc  and  mixed  with  a  sufficient  quantity  of  sulphuric 
acid  previously  diluted  with  one-third  of  its  weight  of  water,  to 
render  the  mixture  fluid.  The  whole  is  allowed  to  stand  for  at 
least  twelve  hours,  in  order  to  effect  the  complete  disintegration  of 
the  animal  tissues.  A  quantity  of  fased  sodium  chloride  is  then 
added  in  large  fragments,  the  flask  connected  with  a  smaller  one  in 
which  are  placed  a  few  crystals  of  potassium  chloi'ate,  and  this 
second  flask  in  its  turn  connected  with  an  absorption  bulb  contain- 
ing water.  Upon  gently  heating  the  contents  of  the  large  flask  and 
continuing  the  application  of  heat  until  the  fragments  of  sodium 
chloride  have  quite  disappeared,  chloride  of  arsenic  distils  over  ; 
and  this,  by  the  action  of  the  chlorine  evolved  from  the  potassium 
chlorate,  is  converted  into  arsenic  acid,  which  collects  in  the  ab- 
sorption bulb.  The  distillate  may  then  be  examined  by  ^Marsh's 
test  or  any  of  the  usual  methods.  The  author's  report  is  a  lengthy 
one,  embodying  minute  details  of  all  the  operations  involved.  A 
blank  experiment  with  the  same  quantities  of  the  reagents  to  be 
employed  is  recommended,  for  ascertaining  their  absolute  freedom 
from  arsenic. 

Determination  of  Phosphorus  in  Forensic  Analyses.    0.  Schif  f  er- 
decker.     (Zeitschr.  des  cesterr.  Aiioth.-Ver.,  1876,  299.)     The  author 


20  YEAR-BOOK    OF    PHARMACY. 

has  made  a  series  of  espcriments  with  the  view  of  ascertaining  to 
"U-hat  extent  Mitscherlich's  process  for  the  detection  of  free  phos- 
phorus may  be  available  for  its  quantitative  estimation.  He  found 
that  if  the  distillation  be  carried  on  to  the  complete  termination  of 
laminosity,  about  three-fourths  of  the  phosphorus  present  will  be 
found  in  the  distillate.  The  contents  of  the  receiver  are  treated 
with  chlorine  to  convert  the  phosphorus  into  phosphoric  acid,  which 
is  then  pi'ecipitated  by  a  mixture  of  magnesium  sulphate,  ammo- 
nium chloride,  and  ammonium  hydrate.  The  precipitate,  when 
washed,  dried,  and  ignited,  contains  in  100  parts  46"2  parts  of 
phosphorus. 

Ergotinuie.  M.  Tanret.  (Journal  cle  P}iarm.,Seipt., 1870.)  Pro- 
fessor Dragendorff's  statement  that  Tanret's  ergotinine  was  not  a 
chemically  distinct  substance,  but  a  mixture  owing  its  activity  to 
the  presence  of  sclerei'ythrin  (see  Year-Book  of  Pharmacy,  1876, 
98,  250),  is  contradicted  by  the  author,  who  supplies  the  following 
evidence  to  show  that  his  ergotinine  cannot  contain  even  a  trace 
of  sclererythrin.  Sclererythrin  is  a  red  substance,  forming  with 
alcohol  and  ether  solutions  an  intense  reddish  yellow  colour.  The 
least  trace  of  it  is  sufficient  to  give,  with  dilute  akalies,  "  a  beautiful 
murexid  colour.-'  Ergotinine,  however,  is  nearly  coloxirless,  and  does 
not  produce  any  coloration  with  alkalies.  If  an  alkaline  solution  of 
sclererythrin  is  treated  with  an  acid,  and  shaken  with  ether,  the 
colouring  matter  passes  into  the  ether.  The  contrary  takes  place  with 
ergotinine  ;  acids  remove  it  from  its  solution  in  ether.  The  violet 
colour  Avhich  sulphuric  acid  produces  with  scleroiodin  cannot  be 
confounded  with  that  characteristic  of  ergotinine.  Sulphuric  acid 
alone  strikes  with  the  latter  only  a  gi'eenish  blue.  In  order  to 
develop  the  reddish  yellow  colour,  followed  by  an  intense  violet  blue 
(see  Ycar-Boolc  of  I'liarmacy,  1876,  98),  it  is  necessary  that  the  acid 
should  not  be  too  concentrated,  but  diluted  with  about  one-eighth 
of  water.  Ergotinine  is  soluble  in  alcohol,  chloroform,  and  ether, 
in  which  scleroiodin  is  insoluble. 

The  author  regrets  that  Prof.  Dragendorff  has  not  given  more 
explicit  details  as  to  the  preparation  and  properties  of  the  bodies  re- 
presented by  him  as  being  the  active  principles  of  ergot,  scleromucin, 
and  sclerotic  acid. 

Ergotine.  Prof  Buchheim.  (From  the  KUnisclie  Wochen- 
schrift;  Pharm.  Journ.,  3rd  series,  vi.,  4.)  Like  other  investi- 
gators, the  author  has  failed  in  his  attempts  to  isolate  the  active 
principles  of  ergot.  He  has  arrived  at  the  conclusion  that  such 
an  isolation  is  impossible,  and  that  for  practical  medical  purposes 


PHARMACEUTICAL    CHEMISTRY.  21 

the  infusion  of  ergot,  or  the  freshly  prepared  cxti-act,  will  alone 
remain  available.  The  organization  of  the  ergot  fungus  seems 
to  him  so  low  that  its  myceUiim  cannot  build  up  organic  matter, 
so  as  to  constitute  an  alkaloid  or  glucoside  substance,  from  water, 
carbonic  acid,  and  ammonia,  but  feeds,  so  to  speak,  more  directly 
on  the  vegetable  material  of  the  mother  plant.  He  believes  that 
less  elementary  compounds  are  taken  np  by  it  from  the  rye 
grain,  and  thinks  the  gluten  the  most  likely  material  from 
which  to  form  the  gelatine-like  substance  which  he  isolated  partly 
from  ergotine.  On  this  modified  albuminous  constituent  of  the 
rye,  at  a  certain  stage  of  its  metamorphosis,  he  infers,  depends  the 
peculiar  action  of  the  fresh  infusion  or  extract.  Any  further  com- 
plex chemical  processes  and  reactions  for  the  isolation  of  the  active 
substance  must  necessarily  have  changed  it  so  much  in  its  natural 
course  of  decomposition,  that  it  has  lost  it  efficacy;  in  the  same 
manner,  for  instance,  as  the  decomposing  albuminous  substances  of 
putrid  blood  lose  their  poisonous  effects  when  decomposition  has 
reached  a  certain  jDoint.  The  freshly  prepared  ergotine  seems 
therefore  to  give  alone  a  guarantee  of  success.  For  subcutaneous 
application  it  ought  to  be  carefully  neutralized  by  carbonate  of  soda, 
as  it  contains  much  acid,  especially  lactic  acid,  as  Buchheim  found, 
besides  quantities  of  leucine. 

Amyrin,  the  Principal  Constituent  of  Elemi.  E.  Buri. 
(Neues  Bc2:)ert.  Pharm.,  x:s.v.,  liyo-204:.)  In  his  last  reports  on  the 
chemisti-y  of  elemi,  Prof.  Flilckiger  mentioned  that  bryiodin  of  the 
formula  (C^q  1^16)2  +  '^  -^2  ^'  constituted  only  a  very  small  propor- 
tion of  the  crystallizable  matter  present  in  the  resin,  and  assumed 
that  the  greater  part  consisted  of  amyrin  of  the  formula 
(CiQH^g)2  +  Ho  0,  which  body  the  author  has  more  fully  investi- 
gated. 

Amyrin  is  contained  in  elemi  in  the  form  of  microscopic  prisms, 
which  can  be  separated  from  the  other  ingredients  by  treatment 
with  cold  alcohol,  the  former  being  insoluble  in  that  liquid.  By  re- 
peatedly recrystallizing  the  residue  from  hot  alcohol,  amyrin  is 
obtained  in  colourless  needles,  joined  together  as  globular  aggregates 
of  silky  lustre.  It  melts  at  177°,  but  resolidifies  at  a  much  lower 
temperature.  Water  does  not  dissolve  it,  but  ether,  chloroform, 
and  carbon  bisulphide  dissolve  it  easily.  Experiments  have  shown 
that  100  parts  of  alcohol  dissolve  3"627  parts  of  amyrin  at  10°. 
Concentrated  sulphuric  acid  dissolves  amyrin  with  a  reddish 
colour.  It  is  not  attacked  by  melting  potash.  An  alcoholic 
solution  of  amyrin  rotates  the  plane  of  polarized  light  to  the  right. 


11  YEAR-EOOK    OF    PHARMACY. 

The  rotation  in  a  layer  200  mm.  long  was  equal  to  +  4'5°at  IC. 
Sp.  gr.  of  the  solution  at  1G°  =  0-8255. 

Amyrin  is  not  volatilized  in  the  vapour  of  water  at  the  ordinary 
atmospheric  pressure.  When  heated  in  a  retort,  it  melts  and  de- 
composes, giving  at  200°  a  yellow,  thin,  oily  distillate,  which  becomes 
thicker  as  the  temperature  rises.  The  distillate  afterwards  solidifies; 
and  at  the  end  yellow  clouds  ascend,  which  condense  in  the  neck  of 
the  retort  to  a  yellow  powder,  leaving  behind  a  shiny  blistered  cake. 
On  heating  a  thin  layer  very  carefully,  amyrin  sublimes  in  long  thin 
needles ;  but  the  yield  is  only  very  small.  Amyrin  dried  at  100° 
gave,  by  analysis,  81'31  to  SS'TT  per  cent,  carbon,  and  ll'oO  to  ll'Sl 
hydrogen,  agreeing  nearly  with  the  formula  Cj  Hj^  0,  which  re- 
quires 63-80  C,  11-73  H,  and  4-47  0. 

An  atom  of  hydrogen  in  the  molecule  of  amyrin  can  be  replaced 
by  the  radical  of  acetic  acid.  One  part  of  amyrin  was  heated  with 
about  four  parts  of  acetic  anhydride  in  a  sealed  tube  to  150°  for 
several  hours,  and  the  residue  dissolved  in  hot  alcohol  and  recrystal- 
lized,  when  acetyl-amyrin  Avas  obtained  in  white  micaceous  laminge. 
It  melts  at  lt'8',  and  solidifies  a  few  degrees  lower.  It  is  more 
difficultly  soluble  in  alcohol  then  amyrin.  At  18°,  lOU  parts  of 
alcohol  dissolve  0-473  part  of  acetyl-amyrin.  Analysis  gave  80-71 
to  81-23  per  cent.  C,  and  10-90  to  10-97  H,. agreeing  with  the 
formula  C,;  H^  0,,  or  C.-  H^^  (C.  H.  0)  O,  which  requires  81  C, 
11  H,  and  8  0. 

Bromine  acts  energetically  on  solid  amyrin,  forming  a  blackish 
green  mass  with  strong  evolution  of  hydrobromic  acid.  A  cold 
saturated  alcoholic  solution  of  amyrin  was  treated  with  an  excess  of 
bromine,  a  yellow  precipitate  being  deposited  after  several  hours, 
which  was  recrystallized  from  hot  alcohol.  The  purified  product 
forms  a  colourless,  indistinctly  crystalline  powder,  which  melts  at  130° 
with  decomposition.  The  analysis  of  this  body  gave  2982  to  30-10 
percent,  bromine,  59-58  to  59-67  carbon,  and  795  to  8-17  hydrogen, 
numbers  which  may  be  represented  approximately  by  either  of  the 
formulae,  C^q  Hj,  Br3  0  and  C,o  Hgj  Brg  0 ;  the  former  requiring 
60-07  per  cent.  C,  7-89  H,  30-04  Br,  and  200  0;  the  latter  5963 
C,  8-11  H,  29-96  Br,  and  200  0.  The  formation  of  these  com- 
pounds may  be  represented  by  the  equations: — 

8  (0,5  H,.  0)  +  30  Br  -  5  (C,,,  H^g  Br.5  0)  +  15  H  Br  +  3  H.  0 ; 
8  (€,,  H,,  0)  ~  20  Br  =  5  (C,o  H,,  Br,  0)  +  5  H  Br  +  3  H,  0. 

Boiling  nitric  acid  forms  with  amyrin  a  clear  yellow  solution,  which 


PHAR5IACEUTTCAL   CHEMISTRY. 


23 


after  evaporation  leaves  a  yellow  mass.  This  mass  gives  an  acid  solu- 
tion in  water,  as  it  contains  oxalic  acid.  It  reduces  Feliling's  solution 
when  warmed.  The  greater  part,  however,  is  not  soluble  in  water; 
it  forms  a  resiu  acid,  which  when  boiled  with  alcohol  deposits,  after 
cooling,  a  yellow  powder.  Dry  hydrochloric  gas  does  not  act  on 
amyrin  alone,  or  dissolved  in  chloroform. 

The  destructive  distillation  of  amyrin,  yielded  the  following  pro- 
ducts : — 

1.  A  fraction  distilling  at  60°  -  70^.  This  formed  a  colourless 
liquid,  lighter  than  water,  almost  tasteless,  and  with  pleasant  smell, 
and  giving  by  analysis  So'lo,  and  (2)  83-47  per  cent,  carbon,  and 
14'.50  to  14-75  hydrogen. 

•2.  A  fraction  distilling  at  185''  -  200°  was  a  yellow  thin  liquid, 
sparingly  soluble  in  water,  with  pleasant  smell  and  aromatic  taste, 
and  giving  by  anyalsis  81'65  per  cent.,  11*47  H,  and  658  0. 

3.  A  fraction  distilling  at  260°  -  280°  was  a  golden  yellow  thick 
liquid,  with  slight  smell  and  sharp  taste,  insoluble  in  water,  and 
giving  84-40  C,  11-56  H,  and  4-04  0. 

4.  Above  300°,  a  thick  liquid  with  brown  colour  distilled  over. 
The  yellow  powder  observed  at  the  end  of  the  distilling  operation 
consisted  of  three  different  bodies,  which  could  not  be  separated  and 
purified. 

The  comparison  of  amyrin  with  icacin,  recently  described  by  Sten- 
bouse  and  Groves  {Lieb.  Ann.,  clsxx.,  253)  as  a  body  contained  in 
the  incense-tree,  is  worthy  of  notice,  as  Fliickiger  assumes  it  to  be 
an  clemi  resin.  It  melts  at  175°.  Stenhouse  and  Groves  give  the 
foi-mula  C^g  H-Q  0  ;  bnt  Fliickiger  thinks  it  probable  that  this  body 
is  similar  to  amyrin,  and  accordingly  deduces  from  his  analyses  the 
formula  C^-  F-^  0  =  (C5  H3)  g  +  H^  O.  Icacin  seems  to  replace  amyrin 
in  some  kinds  of  elemi. 

If  Prof.  Fliickiger's  formula  be  adopted,  we  obtain  the  following 
series  of  elemi  constituents  : — 

Volatile  Oil (C^  Hg;. 

Icaciu (C5H8)9^-IL,6 

Amyrin (CjHgjj  +  HjO 

Bryoidiii (CjHs)4  +  3HoO 

The  Action  of  Dilute  Nitric  Acid  on  Brucine.  W.  A.  Sheustonc. 
(From  a  paper  read  before  the  Pharmaceutical  Society,  Febi-uary  7th, 
1877  ;  Pharm.  Jotirn.,  3rd  series,  vii.,  652,  653.)  The  results  of  the 
author's  experiments  fully  confirm  those  published  last  year  by 
Mr.  Cownley  (Year-Booh  of  PJiarmacij,  1876,  28),  and  disprove  Prof. 


-  i  YEAR-BOOK   OF    THA-RMACY. 

Sonnensclieiu's  allegation  that  bruciiic  can  be  converted  into  strycli- 
nino  by  the  action  of  dilute  nitric  acid  (Year-Boole  ofPharmacij,  1875, 
-2).  It  further  appears  from  Shenstone's  research  that  traces  of 
strychnine  are  readily  destroyed  by  the  action  of  even  very  dilute 
nitric  acid,  and  this  fact  probably  explains  why  Prof.  Sonnenschein 
■failed  to  detect  strychnine  in  the  brucinc  experimented  Avith.  The 
desti'uction  of  strychnine  by  niti'ic  acid,  moreover,  is  an  imj^ortant 
point  in  forensic  investigations. 

^Ir.  Shenstone  also  gives  a  method  of  purifying  brucine,  "svhich 
depends  upon  the  fact  that  strychnine  precipitates  brucine  from  its 
salts,  and  consists  in  partially  precipitating  the  brucine  from  its 
salts  with  an  alkali,  standing  aside  for  a  few  houi-s,  collecting,  wash- 
ing, and  redissolving  the  precipitate  in  a  dilute  acid,  then  again 
partially  precipitating,  etc.  The  author  found  that  the  bruicne  tested 
gave  no  indication  of  strychnine  after  four  precipitations.  The  cost 
of  this  purification  need  be  but  slight,  as  the  unprecipitated  brucine 
can  be  recovered. 

Note  on  Acetate  of  Morphine.  M.  Merck.  (PharuK  Zeitinuj, 
1870.)  When  freshly  prepared  acetate  of  morphine  is  easily  and 
completely  soluble  in  water ;  but  it  soon  becomes  less  soluble,  owing 
to  a  continual  though  slow  elimination  of  acetic  acid,  which  leads  to 
the  formation  of  a  basic  salt  and  eventually  of  pure  morphine.  It  is 
further  altered  by  long  keeping,  becoming  yellow  and  even  brown. 
The  property  of  forming  a  colourless  solution  in  cold,  concentrated 
Rulpburic  acid  belongs  to  the  recently  prepared  salt  only.  After 
it  has  been  kept  for  a  few  weeks  it  yields  a  faintly  coloured  solution, 
although  the  salt  itself  may  still  be  perfectly  white;  aud  the  longer 
it  is  kept  the  darker  will  be  its  solution  in  the  acid.  The  best 
sample  of  commercial  acetate  of  morphine  will  not  dissolve  without 
coloration  in  sulphuric  acid. 

Experience  has  shown  that  acetate  of  morphine  undergoes  no  loss 
of  its  medicinal  properties  through  the  decomposition  referred  to, 
unless  an  intense  yellow  colour  shows  that  the  decomposition  has 
proceeded  too  far.  The  author  thinks  that  the  test  by  means  of 
sulphuric  acid  may  be  abandoned  without  disadvantage,  and  the 
more  so  as  it  may  sometimes  lead  to  the  impression  that  narcotiue  is 
present. 

Note  on  Capsaicin.  J.  C.  Thresh.  (From  a  paper  read  at  the 
Pharmaceutical  Society's  meeting,  December  G,  187G.)  The  author 
has  succeeded  in  obtaining  the  active  principle  of  capsicum  fruit  in 
a  suflSciently  pure  state  for  an  ultimate  analysis.  The  process  of 
purification  consisted  in  dissolving  the  crude  capsaicin  in  solution  of 


rnARJIACEUTICAL    CHEMISTRY.  25 

potash  (official  strength),  and  prcclpitatiDg  by  carbonic  acid ;  col- 
lecting the  precipitate,  washing,  drying,  and  dissolving  in  hot 
petroleum.  After  several  days  the  principle  crystallized  out,  and 
was  washed,  dissolved  in  alcohol,  diluted  with  water,  and  left  ex- 
posed to  the  air  but  excluded  from  dust  until  most  of  the  alcohol 
had  disappeared  and  the  capsaicin  had  crystallized.  This  was  col- 
lected, washed,  and  placed  on  the  water  bath  until  the  weight  was 
constant.  The  combustion  of  the  substance  thus  purified  was 
undertaken  by  Dr.  Buri,  in  Professor  Flilckiger's  laboratory,  and 
gave  the  following  results  : — 

1.  Of  the  capsaicin  dried  over  concentrated  sulphuric  acid,  0'2987 
gram  gave — 

CO.        .        .        0-7713 
R,  6       .         .        0-248G 

2.  0-2860  gram  yielded— 

COo        .        .        0-7363 
H.  6        .         .        0-2347 

From  these  results  are  calculated  the  following  percentages  : — 

I.  II. 

C        .        .         70-42  .  .  70-21 

H        .                   9-25  ,  .  9-12 

0         .         .         20-33  .  .  20-67 

100-  100- 

The  simplest  expression  of  the  constitution  of  capsaicin  is  there- 
fore most  probably  CjH^^Oo,  which  formvila  agrees  very  well  with 
the  above  results. 


90 

.       108 

70-13 

14  H       . 

14 

9-09 

20 

32 

20-78 

lou- 

Having  since  received  a  large  supply  of  alcoholic  extract  of  cayenne, 
Mr.  Thresh  hopes  soon  to  have  a  sufficient  quantity  of  the  pure 
capsaicin  to  attempt  the  discovery  of  its  relationship  to  other 
organic  principles,  and  its  structural  formula. 

Reports  of  the  author's  previous  researches  on  capsaicin  will  be 
found  in  the  Year-Booh  of  Pharmacy,  1876,  250,  543. 

Processes  for  the  Detection  of  Alkaloids.  Prof.  G.  Dragen- 
dorff.     (From  the  American  Chonitst,  April,  1876.) 


26  YEAR-BOOK    OF    PHARMACY. 

The  Stryclmlne  and  Bruchie  Process. 

The  substance  to  be  analysed  should  be  first  cut  into  small  pieces, 
and  treated  with  water  and  a  little  sulphuric  acid,  enough  to  give 
a  decidedly  acid  reaction  to  the  mixture.  To  about  100  c.c.  of  the 
mixture  of  finely-cut  substance  and  water,  add  10  c.c.  of  diluted 
sulphuric  acid  (1"5).  Digest  at  50°  C.  for  several  hours,  and  then 
filter.  Treat  the  undissolved  material  again  with  100  c.c.  of  water 
and  10  c.c.  of  the  dilute  sulphuric  acid  in  the  same  manner,  and 
filter. 

Pat  both  filtrates  together,  and  add  sufiicient  calcined  magnesia 
to  neutralize  most  of  the  free  acid ;  but  the  solution  must  retain 
a  decidedly  acid  reaction.  Evaporate  on  the  water  bath  to  the  con- 
sistency of  thin  syrup,  but  not  to  dryness. 

Mix  this  concentrated  solution  with  three  or  four  times  its  volume 
of  alcohol,  of  from  ninety  to  nine-five  per  cent.,  add  a  few  drops  of 
dilute  sulphuric  acid,  digest  at  from  30°  to  40°  for  twenty-four 
hours,  and  then  filter  off  the  insoluble  matters.  Evaporate  the 
filtrate  until  all  the  alcohol  has  passed  off",  dilute  the  remaining 
solution  to  -50  c.c.  in  a  flask,  and  shake  it  thoroughly  with  from  20 
to  .30  c.c.  of  pure  benzol.  Remove  this  benzol,  and  shake  again 
with  a  fresh  portion. 

After  the  second  portion  of  benzol  has  been  removed,  the  watery 
solution  is  to  be  made  decidedly  alkaline  with  ammonia,  wai'med  to 
40°  or  50°,  when  the  alkaloid  set  free  is  taken  up  by  shaking  again 
thoroughly  with  from  20  to  30  c.c.  of  benzol.  This  is  then  re- 
moved, and  the  shaking  is  repeated  with  another  portion  of  benzol. 

The  benzol  solutions  obtained  in  this  way  are  generally  colour- 
less, and  contain  the  alkaloids  so  nearly  pure  that,  after  shaking 
with  distilled  water  and  clearing  by  immersion  in  warm  water, 
filtering  and  evaporating,  a  residue  is  obtained  in  which  the  alka- 
loids may  be  proved  directly.  But  it  is  better,  after  the  washing 
with  distilled  water,  to  take  up  the  alkaloids  again  by  shaking  with 
water  acidulated  with  sulphuric  acid,  treating  twice  with  20  or  30 
c.c.  of  the  acidulated  water  and  removing  the  benzol,  then  saturate 
the  watery  solution  obtained  in  this  way  with  ammonia,  and  make 
a  new  solution  of  the  alkaloids  in  benzol.  Wash  with  pure  water, 
filter,  and  evaporate ;  and  if  all  the  watery  solution  has  been  re- 
moved from  the  benzol,  the  alkaloids  remain,  in  most  cases,  so 
pure  and  colourless  that  the  identifying  reactions  may  bo  obtained 
directly.  It  is  best  to  divide  the  benzol  solutions  among  several 
watch  glasses,  and  evaporate  at  about  40°  C. 


I 


PHARMACEUTICAL    CHEMISTRY.  27 

The  Go'.iqjlde  Alkaloid  Process. 

1.  Tlie  substance  is  digested  as  above,  witli  water  containing  sul- 
phuric acid,  at  a  temperature  between  40°  and  50°,  two  or  three 
times,  and  the  filtrates  are  put  together  after  all  the  liquid  has  been 
pressed  out  of  the  solid  matter.  Most  of  the  alkaloids  are  not 
injured  by  this  treatment,  even  when  too  much  acid  has  been  used. 
Solanine,  colchicine,  and  digitalin  are  the  only  ones  that  might  be 
injured  by  a  large  excess  of  acid.  If  there  is  abundance  of  time, 
the  macerations  may  be  made  at  common  temperatures. 

Bei'berine  is  less  soluble  in  acidulated  water  than  in  pure  water, 
but  it  is  completely  dissolved  by  the  large  quantity  of  liquid  used. 
Piperine  also  dissolves  with  difficulty  in  acidulated  water,  and  part 
of  this  alkaloid  may  remain  in  the  undissolved  residuum,  where  it 
should  be  sought  for  afterwards. 

2.  Evaporate  the  filtrates,  after  the  free  acid  has  been  partially 
neutralized  with  magnesia,  until  the  liquid  reaches  the  consistency 
of  syrup ;  mix  this  with  three  or  four  times  its  volume  of  alcohol 
and  a  little  dilute  sulphuric  acid,  allow  it  to  digest  for  about  twenty- 
four  hours  at  about  30°,  let  it  become  quite  cold,  and  filter  from  the 
solid  matters  that  have  been  separated  by  the  alcohol.  Wash  the 
solid  residue  with  spirits  of  wine  of  about  seventy  per  cent.  The 
remarks  made  at  1  concerning  solanine,  colchicine,  and  digitalin, 
apply  equally  to  this  digestion. 

3.  The  alcohol  must  be  separated  from  the  filtrate  by  distilla- 
tion (evaporation),  and  the  watery  residue,  after  the  addition  of  a 
little  more  water,  if  necessary,  is  filtered  into  a  flask,  and  in  its 
acid  condition  is  treated  with  freshly  rectified  petroleum  naphtha  (see 
note  at  the  end  of  this  translation)  by  continued  and  repeated 
shaking  together  at  a  temperature  of  about  40°.  After  the  liquids 
have  separated,  the  naphtha,  sometimes  containing  colouring  matter 
and  such  impurities  as  may  be  removed  by  this  treatment,  is  drawn 
off  from  the  aqueous  solution.  The  naphtha  may  also  take  up  piper- 
ine, and  if  a  considerable  quantity  has  been  used,  and  there  is  not 
much  impurity  present,  the  alkaloid  will  be  left  upon  evaporating 
thenaphthain  well-defined  crystals  belonging  to  the  rhombic  system. 
Concentrated  sulphuric  acid  dissolves  it  gradually,  with  the  produc- 
tion of  a  handsome  brown  colour. 

4.  Shake  the  aqueous  solution  with  benzol,  in.  the  same  way,  at 
from  40°  to  50°,  and  evaporate  the  benzol  after  removing  it.  If 
there  are  traces  of  any  alkaloid  in  the  residue  from  this  evaporation, 
it  indicates  caffeine.     In  this  case,  neutralize  the  greater  part  of  the 


28  YEAR-BOOK    OF    PHARJIACY. 

acid  iu  the  aqueous  solution  witli  magnesia  or  ammonia,  but  still 
leave  it  decidedly  acid,  and  treat  it  again  with  fresb  portions  of 
benzol,  until  the  latter  leaves  no  residue  upon  evaporation.  Wasli 
the  benzol  solution  by  shaking  it  vrith  distilled  water ;  separate  from 
the  water,  and  filter  it.  Distil  off  the  greater  part  of  the  benzol 
from  this  filtrate,  and  evaporate  the  remainder  upon  several  watch 
glasses.  Care  must  bo  exercised  that  in  case  a  drop  of  the  aqueous 
fluid  passed  through  the  filter  it  is  not  evaporated  with  the  benzol. 

The  residue  from  this  evaporation  may  contain  caffeine,  delphine, 
colchicine,  cubebine,  digitalin,  and  traces  of  veratrine,  physostig- 
mine,  and  berberine.  Caffeine  forms  definite  crystals,  as  colourless, 
glossy  needles ;  it  is  known  by  its  reaction  with  chlorine  water  and 
ammonia.  Sulphuric  acid  does  not  colour  it.  Cubebine  also  forms 
small  crystals,  which  may  be  known  by  their  behaviour  with  sul- 
phuric acid,  and  the  same  may  be  said  of  colocynthine,  elateriue,  and 
syringine.  A  yellow  coloured  residue  indicates  colchicine  and  ber- 
berine. Sulphuric  acid  dissolves  and  colours  colchicine  an  intense 
and  durable  dark  yellow ;  bei'berine  olive  green,  becoming  clear 
afterwards.  Berberine  may  be  distinguished  from  colchicine  by  the 
behaviour  of  its  alcoholic  solution  with  tincture  of  iodine.  Del- 
phine, digitalin,  veratrine,  and  physostigmine  arc  left  as  amorphous 
nearly  colourless  residues.  Delphine  is  coloured  light  brown  by 
sulphuric  acid ;  digitalin  yields  with  it,  in  less  than  fifteen  hours,  a 
number  of  colours,  changing  from  amber,  through  red  and  brown, 
to  dark  cherry  red,  and  its  presence  may  be  confirmed  by  the  sul- 
phuric acid  and  bromine  reaction.  Veratrine,  with  pure  sulphuric 
acid,  becomes  yellow  orange,  and  in  less  than  half  an  hour  beautiful 
orange  red,  and  this  test  may  be  confirmed  by  boiling  with  fuming 
hydrochloric  acid.  Physostigmine  is  not  coloured  by  sulphuric 
acid.     It  may  be  known  by  its  action  on  the  eyes  of  cats. 

5.  The  acid  watery  liquid  is  shaken  with  amylic  alcohol  in  the 
same  way  as  in  3  and  4,  if  the  presence  of  theobromine  is  suspected. 

There  are  also  taken  up  by  the  amylic  acid  some  of  the  above- 
named  alkaloids  remaining  from  3  and  4;  namely,  veratrine  and 
berberine,  and  traces  of  narcotine,  aconitine,  and  atropine,  and  they 
are  left  in  crystals  after  the  evaporation  of  the  solution. 

Theobromine  is  recognised  by  its  reaction  with  chlorine  water 
and  ammonia,  and  also  as  it  dissolves  without  colour  in  concentrated 
sulphuric  acid. 

Narcotine  is  not  readily  soluble  in  acetic  acid,  and  may  be  re- 
cognised by  its  reaction  when  warmed  with  concentrated  sulphuric 
acid. 


THARMACEUTICAL    CHEMISTRY.  29 

G.  The  acid  watery  liquid  is  shaken  with  chloroform  only  when 
the  presence  of  the  alkaloids  of  opium  is  suspected. 

Chloroform  takes  up  papaverine,  thebaine  (slowly),  together  with 
small  quantities  of  narceine,  brucine,  physostigmine,  berberine, 
and,  when  the  treatment  given  at  5,  is  omitted,  veratrine  and 
narcotine. 

Crystals  of  papaverine  and  brucine  ai-e  left  after  the  evaporation 
of  the  chloroform  solution.  Papaverine  may  be  readily  distinguished 
by  testing  with  sulphuric  acid  (beautiful  blue  violet  colour),  and 
brucine  by  the  red  colour  imparted  to  it  by  Erdmann's  reagent, 
^lost  of  the  narcotine,  thebaine,  narceine,  veratrine,  physostigmine, 
and  berberine,  are  left  as  amorphous  substances. 

IS^arcotine  may  be  separated  from  the  other  alkaloids  by  dilute 
acetic  acid,  in  which,  it  is  not  readily  soluble,  and  it  may  be  proved 
as  in  5.  Thebaine  is  characterized  by  its  behaviour  with  cold  sul- 
phuric acid.     Veratrine  and  physostigmine  as  above. 

7.  The  watery  liquid  at  about  43°  is  then  covered  with  a  layer 
of  petroleum  naphtha,  made  distinctly  alkaline  with  ammonia,  and 
immediately  well  shaken.  After  the  first  naphtha  solution  has  been 
drawn  off,  other  extractions  should  be  made  at  the  same  temperature 
with  fresh  portions  of  petroleum  naphtha.  The  warm  naphtha 
solutions  should  be  washed  with  distilled  water  and  afterwards 
filtered  and  evaporated.  If  the  solution  is  too  highly  coloured  by 
foreign  matter,  it  may  be  purified  by  taking  up  the  alkaloids  in  acid- 
ulated water,  adding  ammonia  and  shaking  with  jsure  naphtha 
again. 

The  petroleum  naphtha  takes  up  strychnine,  brucine,  quinine, 
emetine,  veratrine,  conine,  nicotine,  and  papaverine. 

(a)  Of  these,  conine  and  nicotine  are  fluids,  and  have  characteristic 
odours.  They  may  be  bi'ought  into  solution  in  distilled  water,  and 
nicotine  is  precipitated  in  minute  crystals  by  potash-cadmium- 
iodide  from  the  diluted  solution  after  neutralizing  with  sulphuric 
acid,  while  conine  is  precipitated  in  amorphous  form. 

(b)  Upon  cooling  the  warm  naphtha  solution,  quinine  separates, 
and  traces  of  strychnine  and  papaverine  also  crystallize  out. 

(c)  After  evaporation,  the  remainder  of  the  quinine,  strychnine, 
and  papaverine  are  left  in  crystals,  and  brucine,  emetine,  and  vera- 
ti-ine  in  amorphous  form. 

The  dry  alkaloids  are  treated  with  anhydrous  ether,  which  dis- 
solves quinine,  emetine,  papaverine,  and  veratrine ;  and  also  conine 
and  nicotine,  if  they  have  not  been  removed  by  water. 

Strychnine  and  brucine  may  be  separated  by  absolute  alcobol,  in 


30  YEAR-BOOK   OP    PHARMACY. 

which  strychnine  is  neai'ly  insoluble.  Bracine  is  recogaised  after 
the  evaporation  of  its  solution,  by  its  behaviour  with  Erdmann's  re- 
agent. Strychnine  may  be  determined  by  means  of  sulphuric  acid 
and  bichromate  of  potash. 

After  evaporating  the  ether  solution,  quinine,  emetine,  veratrine, 
and  papaverine  are  dissolved  in  the  smallest  possible  quantity  of 
vei'y  dilute  sulphuric  acid;  and  the  cold  solution,  which  should  not 
contain  less  than  one  per  cent,  of  the  alkaloids,  is  treated  with  car- 
bonate of  soda,  when  quinine,  emetine,  and  papaverine  are  precipi- 
tated. 

Quinine  may  be  determined  by  its  behaviour  with  chlorine  water 
and  ammonia.  Emetine  by  pi'oducing  an  emetic  effect,  and  by  the 
absence  of  the  veratrine  reaction  with  hydrochloric  acid.  Papa- 
verine by  its  behaviour  with  sulphuric  acid.  Veratrine,  after  its 
watery  filtrate  has  been  treated  with  chloroform  and  the  latter 
evaporated  by  boiling,  with  hydrochloric  acid. 

8.  The  alkaline  watery  liquid  is  shaken  with  benzol  at  40°  or  50°, 
purifying  as  in  7.  This  removes  quinidine,  cinchonine,  atropine, 
hyoscyamine,  aconitine,  physostigmine,  and  codeine. 

Crystals  of  cinchonine,  sometimes  accompanied  by  a  little  atropine 
and  quinidine,  separate  from  the  solution  on  cooling. 

After  evaporating  the  solution  there  remain  with  those  just 
named,  crystallized  codeine  (very  distinct),  aconitine,  hyoscyamine, 
and  physostigmine  (mostly  amorphous). 

(a)  The  residue  left  by  evaporation  is  treated  with  ether,  which 
dissolves  all  the  above-named  alkaloids  except  cinchonine. 

(b)  The  residue  from  the  evaporation  of  this  ether  solution  must 
be  dissolved  in  the  smallest  possible  quantity  of  water  containing 
sulphuric  acid,  and  treated  with  ammonia  slightly  in  excess,  which 
separates  quinidine  and  aconitine,  leaving  atropine,  hyosc^'amine, 
and  codeine  in  solution. 

The  precipitate,  which  may  contain  quinidine  and  aconitine,  is 
collected  on  a  very  small  filter  and  dissolved  in  the  least  quantity  of 
hydrochloric  acid.  Upon  the  addition  of  chloride  of  platinum  the 
whole  of  the  quinidine  is  precipitated. 

The  solution  of  aconitine  is  fx'eed  from  platinum  by  a  current  of 
sulphuretted  hydrogen ;  then  it  is  made  alkaline  and  shaken  with 
chloroform.  In  the  residue  left  by  evaporating  this  chloroform 
solution,  the  aconitine  may  be  recognised  by  means  of  sulphuric  or 
phosphoric  acid. 

(c)  Atropine  dissolves  with  diflBculty  in  cold  benzol,  and  codeine 
dissolves  readily.      The  former  is  not  coloured  by  concentrated  sul- 


PHARilACEUTlCAL    CHEMISTRY.  31 

phuric  acid  ;  tlio  latter  is  gradually  coloured  blue.  Atropine,  when 
warmed  witH  concentrated  sulphuric  acid,  gives  the  characteristic 
odour  pi'eviously  described  ;  codeine  does  not.  Atropine  (hyoscja- 
mine)  distends  the  pupil  of  the  eye  ;  codeine  does  not.  For  physos- 
tigmine,  see  4. 

9.  The  watery  liquid  is  now  acidulated  with  sulphuric  acid  and 
heated  to  50°  or  G0°,  covered  with  amyhc  alcohol,  purifying  as  in 
7  and  8.  By  shaking  with  amylic  alcohol  at  the  temperature 
just  given,  the  morphine,  solanine,  and  part  of  the  narceine  are  ob- 
tained. The  latter  should  be  dissolved  in  lukewarm  water,  and  put 
with  the  watery  liquid  at  10. 

The  solution  of  solanine  in  amylic  alcohol  gelatinizes  upon  cooling, 
that  of  morphine  forms  the  best  of  alkaloid  crystals.  Morphine  is 
proved  by  Frohde's  reaction  (with  raolybdate  of  soda)  and  by 
Hersemann's  test  (concentrated  sulphuric  acid  solution  and  nitric 
acid). 

Solanine  is  characterized  by  its  decomposition  in  hydrochloric  acid, 
and  the  retention  of  the  products  of  this  decomposition  by  ether ; 
and  also  by  its  behaviour  with  iodine  water  and  sulphuric  acid. 

10.  The  watery  liquid  may  still  contain  curarine  and  traces  of 
berberine,  narceine  (and  digitalin). 

Evaporate  it  to  dryness  with  powdered  glass  ;  digest  the  pulver- 
ized residue  for  a  day  in  alcohol  ;  filter,  and  evaporate  the  filtrate. 
If  the  residue  is  very  impure,  it  may  be  repeatedly  recrystallized 
from  water  and  alcohol. 

Berberine  remains  as  a  yellow  coloured  residue,  and  is  known  by 
the  behaviour  of  its  alcoholic  solution  with  iodine  water. 

Narceine  is  left  in  colourless  crystals.  It  is  recognised  by  its 
reaction  with  sulphuric  acid,  or  by  the  behaviour  of  its  aqueous 
solution  with  iodine  water. 

Curarine  is  left  mostly  amorphous,  and  is  distinguished  by  its 
reaction  with  sulphuric  acid  alone,  and  with  sulphuric  acid  and 
chromate  of  potash. 

Note. — Petroleum  naphtha  has  a  boiling  point  between  30'  and  80°.  It 
should  be  purified  by  shaking  with  an  ammoniacal  solution  of  acetate  of  lead, 
and  distilling.  That  which  is  sold  in  Kussia  as  an  illuminating  fluid,  under  the 
name  of  "  chandoiiue,"  may  be  rectified  for  use  in  this  way.  Petroleum  naphtha 
does  not  dissolve  asphalt,  which  is  soluble  in  benzol.  Benzol  boils  at  80°  or  81°. 
Petroleum  naphtha  begins  to  boil  at  a  much  lower  temperature. 

Preparation  of  Pure  Caustic  Potash.  M.  Pollacci.  {Zeltsclu-. 
des  oesterr.  Aj^oth.-Ver.,  1876,  299.)  TVohler's  process  (heating  one 
part  of  pure  nitre   with  two  parts  of  metallic  copper)  yields  a  pre- 


S2  YEAR-BOOK    OF    PHARMACY. 

paration  containing  potassium  nitrite  as  "well  as  copper.  The 
author  obtains  a  pnrer  preparation  by  using  iron  filings  in  place 
of  the  copper.  The  products  of  the  decomposition  are  potassium 
oxide,  ferric  oxide,  and  nitrogen.  The  operation  is  conducted  in  an 
iron  crucible. 

The  Pharmacopoeia  Test  of  Guinine  Sulphate.  Dr.  B.  H.  Paul. 
(From  a  paper  read  before  thePliarm.  Soc,  February  7,  1877.)  The 
official  test  depends  upon  the  fact  that  ether  is  capable  of  dissolving 
quinine  freely,  but  cinchonidine  and  chinchoninc  sparingly.  The 
proportion  of  ether  in  the  Pharmacopoeia  is  half  a  fluid  ounce  to 
10  grains  of  the  quinine  sulphate,  and  the  absence  of  any  separation 
of  alkaloid  crystals  after  the  addition  of  ammonia  and  ether  is  stated 
to  be  evidence  of  purity.  This,  however,  is  not  the  case.  Upon 
mixing  one  decigram  (O'l  gram)  of  cinchonidine  sulphate  with 
about  2  c.c.  of  ether,  and  adding  ammonia  sufficient  to  separate  the 
base,  the  presence  of  the  insoluble  alkaloid  becomes  sufficiently 
distinct.  But  when  the  same  quantity  of  cinchonidine  salt  is  mixed 
with  a  lai'ge  proportion  of  quinia,  the  result  is  diflferent,  and  it 
appears  that  the  presence  of  quinine  increases  the  solubility  of  cin- 
chonidine in  ether^  or  at  any  rate  prevents  the  latter  from  separa- 
ting  in  a  crystalline  state.  The  author  has  applied  the  Pharma- 
copoeia test  to  quinine  sulphate,  which  he  ascertained  by  other 
means  to  contain  10  per  cent,  of  cinchonidine  sulphate ;  but  the 
mixture  remained  perfectly  limpid,  and  any  one  ajiplying  the  test 
would  say  that  the  salt  was  absolutely  pure.  The  limit  within 
which  cinchonidine  cannot  be  detected  by  this  process  in  quinine 
is  therefore  much  higher  than  has  been  heretofore  supposed.  Some 
authorities  give  this  limit  as  h  percent.,  others  as  2  and  3  per  cent., 
but  the  writer  is  inclined  to  think  that  less  than  10  per  cent,  cannot 
be  detected.  A  mixture  consisting  of  0"5  gram  of  quinine  sulphate 
and  O'Oo  gram  (10  per  cent.)  of  cinchonidine  sulphate  does  not  show 
a  particle  of  crystallization.  The  quantity  of  ether  recommended  to 
be  used  in  the  B.  P.  is  much  in  excess  of  what  is  needed.  The 
author  states  that  he  has  made  many  mixtures  of  the  two  salts,  and. 
that  even  the  presence  of  30  per  cent,  of  cinchonidine  might  pass 
unnoticed.  But  even  with  much  smaller  quantities  of  ether  it  is 
impossible  to  rely  on  its  use. 

The  plan  which  he  has  adopted  for  detecting  the  presence  of 
cinchonidine  is  that  of  fractional  crystallization,  which  he  finds  to 
give  a  speedy  indication  of  its  presence.  About  30  gi'ains  of  the 
alkaloid  salt  are  put  into  a  capsule,  a  fluid  ounce  and  a  half  of  water 
is  added,  and   heat  is   applied    until  the  salt  is  nearly  dissolved. 


PHARMACEUTICAL   CHEMISTRY.  33 

The  water  is  insufficient  to  dissolve  it  entirely  ;  but  "when  heated  up 
to  the  boiling  point,  the  greater  part  of  th.e  quinine  sulphate  is  dis- 
solved. Upon  cooling,  most  of  the  latter  is  deposited,  and  the  more 
soluble  cinchonidine  sulphate  remains  in  solution.  The  liquid 
portion  is  then  a  saturated  solution  of  quinine  sulphate,  together 
with  any  cinchonidine  that  may  be  present.  By  applying  the  test 
to  that  liquid,  an  indication  may  be  got  of  cinchonidine,  if  present. 
This  is  a  modification  of  the  test  which  has  been  very  much  used 
on  the  Continent,  known  as  Kerner's  test,  and  the  one  adopted  in  the 
G.  P.  The  latter  consists  in  adding  20  c.c.  of  distilled  water  at 
15°  C,  to  2  grams  of  the  salt,  briskly  .shaking,  and  filtering  after 
thirty  minutes  at  15°  C.  Five  c.c.  of  the  filtrate  are  put  into  a  test 
tube,  and  7  c.c.  of  ammonia  are  poured  carefully  on  the  top.  The 
tube  is  closed  -with  the  finger  and  gently  reversed,  when  either 
immediately,  or  in  a  short  time,  the  contents  of  the  tube  will  form  a 
perfectly  limpid  solution,  if  the  salt  was  pure.  This  test  is  very 
reliable,  and  founded  on  very  sound  principles,  which  are  these : — 
Quinine  sulphate  is  sparingly,  but  cinchonidine  sulphate  readily, 
soluble  in  water,  of  which  the  former  requires  750,  the  latter  100 
parts  ;  so  that,  putting  these  two  facts  together,  a  very  good  indica- 
tion is  obtained  as  to  the  presence  or  absence  of  cinchonidine.  The 
defect  attaching  to  this  test  lies  in  its  application.  If,  for  instance, 
a  sample  of  quinine  sulphate,  or  a  mixture  containing  1  per  cent,  of 
cinchonidine  sulphate,  be  treated  with  cold  water,  and  the  cold 
filtrate  be  treated  with  an  equal  volume  of  ammonia  (sp.  gr.  0"920), 
the  result  is  a  perfectly  clear  solution.  But  when  the  same  salt  is 
boiled  with  water,  and  even  when  treating  the  cold  liquid  with  ether, 
the  cinchonidine  will  separate. 

In  an  examination  of  nine  samples  of  quinine  sulphate,  the  author 
found  cinchonidine  present  in  all  cases  ;  varying  in  amount  from 
1  to  10  per  cent. 

Between  these  two  extremes  of  1  and  10  per  cent,  there  is  a  very 
wide  margin  ;  and  the  author  thinks  that  the  circumstance  that  such 
quantities  may  be  overlooked  in  testing  quinine,  is  important  both 
to  manufacturers  and  to  pharmacists,  who  are  liable  to  be  placed  in 
circumstances  of  difficulty  on  account  of  this  impurity.  In  the  first 
place,  a  manufacturer  who  produced  a  pure  article  might  be  pre- 
judiced, in  tendering  for  contracts,  by  being  placed  in  disadvan- 
tageous competition  with  other  persons  who  offered  quinine  of  the 
character  mentioned,  containing  10  per  cent,  of  cinchonidine,  a 
proportion  amounting,  at  the  present  prices,  to  a  difference  of  ten- 
pence  on  the  ounce,  which  is  a  large  extra  profit  on  the  quinine. 

D 


34 


YEAR-BOOK   OF    PHARMACY. 


The  process  employed  by  the  author  for  the  analysis  of  the  nine 
samples  was  as  follows : — Four  or  five  grams  of  the  dried  salt 
were  dissolved  in  80  to  150  c.c.  of  boiling  water ;  when  cold  the 
clear  liquid  was  removed  from  the  crystallized  quinine  sulphate,  and 
shaken  with  ether  so  as  to  leave  a  distinct  layer  undissolved.  On 
the  addition  of  ammonia  in  excess,  the  alkaloid  separated  was  in 
most  cases  only  partially  soluble  in  the  ether ;  with  the  samples 
containing  least  cinchonidine,  the  whole  of  the  alkaloid  was  at  first 
dissolved  by  the  ether,  but  after  the  lapse  of  a  few  hours  the  cin- 
chonidine was  deposited  in  the  form  of  crystals,  which  were  col- 
lected on  a  filter  and  weighed.  The  quinine  sulphate,  which 
separated  on  cooling  the  hot  solution,  was  again  treated  as  at  first, 
and  the  mother-liquor  again  mixed  with  ether  and  ammonia.  In 
this  way  a  further  quantity  of  alkaloid  insoluble  in  a  moderate 
proportion  of  ether  was  obtained ;  and  by  repeating  the  process  a 
third  time  another  small  quantity  was  extracted.  The  samples  were 
all  dried  at  212°  F.  in  a  weighing  glass  capable  of  being  perfectly 
closed  immediately  on  being  removed  from  the  steam  bath.  The 
results  in  all  cases  indicate  the  minimum  quantity  of  cinchonidine 
which  the  process  could  indicate. 


Water  of 

Cinchonidine  Sulphate. 

Sample. 

Crystallization. 

Dry. 

Equal  to  Crystallized. 

1 

150.5 

7-98 

919 

2 

15-51 

7-51 

8-64 

3 

14-90 

4-22 

4-86 

4 

15-04 

5-92 

6-81 

5 

14-20 

•99 

1-14 

6 

15-15 

3-16 

3-64 

7 

13-07 

4-90 

5-64 

8 

8-10 

4-55 

5-24 

9 

10-37 

5-44 

6-26 

Examination  of  Some  Commercial  Samples  of  Citrate  of  Iron  and 
Cluinine.  Dr.  B.  H.  Paul.  (P^arm.  Jowra.,  3rd  series,  vii.,  829.) 
The  British  Pharmacopoeia  requires  this  preparation  to  contain  IG 
per  cent,  of  dry  quinine,  and  the  application  of  the  test,  as  generally 
performed,  is  more  apt  to  yield  figures  in  excess  than  below  the  true 
per  centago,  owing  to  the  reluctance  with  which  the  precipitated 
quinine  parts  with  its  water.  Dr.  Paul  examined  three  samples  of 
the  salt.  The  first  was  contained  in  a  1  oz.  bottle,  bearing  the  label 
of  a  wholesale  druggist  in  London,  with  the  name  and  address  of 


PHARMACEUTICAL    CHEMISTRY.  35 

Mie  firm,  and  describing  the  preparation  as  "  Citrate  of  Iron  and 
Quinine,  Britisli  Pharmacopoeia."  On  testing  this  sample  accord- 
ing to  the  oflBcial  directions,  it  gave  a  precipitate  amounting  to  9"3 
per  cent.,  instead  of  16  per  cent.,  or  a  little  more  than  one  half  of 
what  it  should  have  been.  Oa  testing  this  sample  by  another 
method,  and  carefully  extracting  the  alkaloid  by  ether,  the  total 
amount  of  the  dry  alkaloid  was  8"96  per  cent.  A  further  examin- 
ation of  this  alkaloid  showed  that  it  was  not  entirely  quinine,  but 
that  nearly  one-fourth  of  it  consisted  of  cinchonidine,  with  some 
amorphous  alkaloid  and  cinchonine.  The  actual  proportions  were 
as  follows : — 

Qvxinine 6-80 

Other  alkaloids 2-16 

8-96 

Sample  No.  2  was  also  in  a  1  oz.  bottle,  and  bore  a  similar  label 
and  seal  to  No.  1.  By  the  Pharmacopoeia  test  this  sample  assayed 
11" 7  per  cent.  When  tested  with  ether,  the  dry  alkaloid  extracted 
in  this  way  amounted  to  9"7  per  cent.,  and  on  further  examination 
of  this  alkaloid  it  proved  to  contain,  as  in  the  previous  instance, 
other  alkaloids  besides  quinine;  the  actual  figures  being  as 
follows: —  ■ 

Qumine 7-08 

Other  alkaloids 2-62 

9-70 

Sample  No.  3  was  received  in  a  paper  package,  and  had  already 
become  somewhat  damp.  When  tested  by  the  Pharmcopoeia  me- 
thod it  gave  a  precipitate  which  in  drying  gave  indications  that  it 
was  not  quinine.  This  precipitate  amounted  to  8"87  per  cent. 
The  alkaloids  extracted  from  this  sample  by  treatment  with  ether 
and  thorough  drying  amounted  to  6'96  per  cent.,  and  this  consisted 
chiefly  of  amorphous  alkaloids,  namely  : — 

Quinine 1'60 

Other  alkaloids 5*36 

6-96 

The  fact  that  in  two  cases  the  preparations  here  refei'red  to  pro- 
fessed to  be  in  accord  with  the  requirements  of  the  Pharmacopceia, 
rendei's  these  results  especially  noteworthy. 

The  Water  of  Crystallization  in  duinine  Sulphate.  A.  J. 
Cownley.  (Pharm.  Joum.,  3rd  series,  vii.,  189.)  Whilst  the 
quantity  of  water  of  crystallization    existing  in  freshly   prepared 


36  TEAR-BOOK    OF    PHARMACY. 

and  uneflBoresced  quinine  sulphate  is  enveloped  in  some  doubt, 
owing  to  the  efflorescent  character  of  this  salt  of  quinine,  and  the 
question  whether  it  contains  7  molecules  of  water  according  to 
Reynault,  7h  as  given  by  Jobst  and  Hesse,  or  8  molecules  as 
stated  by  Schorlemmer,  has  still  to  be  determined,  it  seems  to  be 
very  generally  stated  that  the  anhydrous  sulphate  in  only  obtained 
at  a  temperature  exceeding  120°  C. 

Jobst  and  Hesse,  as  quoted  by  Watts,  state  that  at  110°  to 
120°  C.  the  salt  loses  the  whole  of  its  water  of  crystallization  ;  and 
the  same  temperature  by  Millon  and  Coumaille,  as  well  as  in  Huse- 
n-'ann's  "  PflanzenstofFe "  for  1870,  with  the  additional  statement 
that  at  100°  C.  the  sulphate  contains  2  molecules  of  water.  This 
latter  view,  and  the  opinion  that  the  salt  is  then  identical  with  the 
air-dried  salt  as  regards  hydration,  seem  to  have  been  adopted  as 
correctly  representing  the  condition  of  quinine  sulphate  at  that 
temperature. 

The  author's  experiments  show  that  quinine  sulphate  really  be- 
comes anhydrous  at  100°  C,  and  when  freely  exposed  to  the  air  in 
this  condition  it  rapidly  absorbs  water  until  it  has  the  composition 
of  a  sulphate  with  2  molecules  of  water ;  but  when  the  access  of  air 
is  retarded,  the  water  of  crystallization  is  of  a  varying  quantity,  and 
bears  no  constant  relation  to  the  salt  until  2  molecules  have  been 
absorbed  ;  also  that  freshly  prepared  quinine  sulphate  probably  does 
contain,  as  stated  by  Jobst  and  Hesse,  7|  molecules  of  water,  and 
that  the  salt  in  this  condition,  when  freely  exposed  to  air,  rapidly 
effloresces  until  it  attains  the  composition  of  a  sulphate  with  2  HoO. 

Aricine  and  Allied  Substances.  0.  Hesse.  {Journ.  Chem. 
Soc;  from  Lichig's  An7ialen,  clxxxi.,  o8.)  The  author  reviews  the 
experiments  made  by  Pelletier  and  Coriol,  in  1829,  on  a  bark  of 
doubtful  cinchona  nature,  from  which  these  chemists  obtained  a 
base  crystallizing  in  white  transparent  crystals,  soluble  in  alcohol 
and  ether,  insoluble  in  water,  and  capable  of  forming  an  acid  and  a 
neutral  sulphate ;  also  those  by  Leverkohn,  who  obtained  from  false 
cali.saja  bark  (cinchona  from  Cusco)  a  gelatinous,  apparently  non- 
crystalline, sulphate  of  a  base  termed  by  Buchner  cusconine ;  those 
by  Manzini,  who  extracted  from  pale  tenchina  bark  an  alkaloid  which 
he  called  cinchovatine,  but  which  the  author  subsequently  found  to 
contain  also  cinchonine,  and  which  was  subsequently  found  by  H. 
Bourchardat  and  Winckler  to  be  identical  with  aricine;  and  finally 
those  byDavid  Howard,  whose  results  the  author  considers  to  be  due 
to  his  having  obtained  an  impure  jiar/ci'«e  (containing  cinchonine?). 

The  alkaloids  of  a   Cusco  bark  obtained  from  De  Vrij  were  ex- 


PHA.RMACEDTICAL    CHEMISTRY.  37 

tracted  by  the  author  in  the  ordinary  way ;  the  concentrated  neutral 
sulphuric  acid  solution  yielded  crystals  of  cinchonidine  suljihate, 
and  then  gelatinized  to  a  mass  of  microscopic  prisms  of  the  same, 
containing  a  little  quinine  sulphate;  the  filtrate  from  these  contained 
cinchonine  and  amorphous  bases,  from  which  nothing  characteristic 
could  be  isolated.  Other  samples  of  Cusco  bark  yielded  only  cin- 
chonidine and  traces  of  amorphous  bases ;  the  author  considers  De 
Vrij's  bark  not  to  have  been  genuine  Cusco  bark.  Another  Cusco 
bark  {China  de  Cusco  vera  of  Wiggers),  identical  with  that  employed 
by  Pelletier  and  Coriol,  yielded  cinchonine,  a  little  cinchonidine, 
and  amorphous  bases,  but  no  other  crystallizable  alkaloid. 

Commercial  "pale  tenchina"  bark,  carefully  examined  and  selected 
by  Wiggers,  yields  no  cinchovatine  or  aricine,  but  only  cinchonine 
and  traces  of  quinidine  (the  conchinine  of  the  author)  and  amor- 
phous bases.  Other  pale  tenchina  barks  from  France  yielded 
cinchonidine  also ;  but  this  bark  appeared  to  contain  an  admixture 
of  other  varieties,  although  specimens  could  be  readily  picked  out 
agreeing  in  all  respects  with  the  sample  obtained  from  Wiggers. 

Cinchovatine,  prepared  by  Winckler  and  examined  by  the  author, 
gave  no  blue  fluorescence  when  dissolved  in  sulphuric  acid ;  it 
formed  fine  white  prisms,  which  gave  numbers  agreeing  with  those 
required  for  cinchonidine;  it  melted  at  208°  (not  corrected),  and 
gave  the  rotation  (a)^  —  - 107'25,  whilst  pure  cinchonidine  melts 
at  205°  (not  corrected),  and  gives  the  rotation  (a.)^  =  106  89  under 
the  same  conditions.  It  gave  a  hydrochloride  indicated  by  Cog  Ho^ 
N'a  O.  H  CI.  Hg  0  ;  a  platinum  salt,  Coq  H^^  N.  0.  2  H  CI.  Pt  Cl.^;  a 
sulphate  (C20  H^^  NoO)^  H3  S  0,j,  anhydrous  after  drying  in  the  air, 
and  giving  the  rotation  (a)^  =  -  172'20,  whilst  pure  cinchonidine 
sulphate  gave  (a)^  -  -172"37  ;  and  finally,  the  hydrochloride  and 
the  sulphate  gave  with  phenol  water  compounds  precisely  resembling 
those  obtained  with  cinchonidine. 

Aricine  sulphate  of  commerce  consisted  mainly  of  a  sulphate 
forming,  on  recrystallization,  a  gelatinous  mass  of  minute  needles, 
together  with  some  cinchonine  and  quinine  sulphates  and  a  trace  of 
resinous  matter  insoluble  in  water.  The  base  in  these  small  crystals 
gave  on  analysis  numbers  agreeing  with  cinchonidine ;  it  melted  at 
205°,  and  gave  the  rotation  (ffl)d  =  - 107-25 ;  the  sulphate  crys- 
tallized from  a  large  bulk  of  water  formed  ciystals  containing 
(C20  HojNj  0)3  H,  S  0^.  3  H2  0  ;  with  phenol  water  and  Seignette 
salt  it  formed  difiicultly  soluble  compounds  precisely  agreeing  in 
all  respects  with  those  from  cinchonidine. 

Hence  the  author  concludes  that  the  bodies  described  as  aricine 


OO  YEAR-BOOK    OF    PHARMACY. 

and  ciiicliOTatine  are  simply  more  or  less  pure  cinchonidine,  as  is 
also  a  la^vo-rotatorj  crystalline  base  extracted  in  1873,  by  De  Vrij, 
from  Jamaica  bark. 

Oil  of  Parsley.  E.  von  Gericliten.  (Ber.  der  deutsch.  Ghem.- 
Ges.,  ix.,  258-2G0.)  The  oil  examined  by  the  author  was  supplied 
by  Dr.  TrommsdorfF,  who  obtained  from  15  kilos,  of  parsley  fruit 
90  grams  by  distillation,  and  10  grams  more  by  shaking  the  distillate 
with  benzol.  It  commenced  to  boil  at  160°  C,  nearly  all  the  terpene 
having  come  over  below  210^.  Between  270°  and  290°  a  heavy 
yellowish  green,  very  refractive,  nncrystallizable  liqaid  was  obtained, 
and  above  300°  C.  several  brown  decomposition  products.  By  re- 
peated rectification  of  the  first  portion,  the  pure,  colourless  terpene 
was  obtained,  boiling  between  160°  and  164°  C,  and  having  an 
intense  odour  of  parsley.  Its  specific  gravity  at  12°  C.  is  '865,  and 
its  rotation  power  for  yellow  light  and  a  column  of  100  mm.  =  — 
30"8°.  Muriatic  acid  colours  it  gradually  brown,  and  destroys  the 
parsley  odour.  Terpin  and  solid  chlorhydrates  could  not  be 
obtained. 

Apiol.  E.  von.  Gerichten.  (Ber.  der  deutsch.  Chem.-Ges.,  ix., 
1477-1479.)  Pure  apiol,  or  parsley-camphor,  forms  long,  white, 
brittle  needles,  melting  at  30°  and  boiling  at  about  300°.  On  boiling 
it  with  alcoholic  potash,  it  is  converted  into  a  body  crystallizing  in 
pearly,  rhombic  plates,  melting  at  53"5°,  and  containing,  as  a  mean 
of  three  combustions,  C  =  65  4,  H  =  5*5.  On  boiling  it  with  dilute 
nitric  acid,  it  yields  oxalic  acid  and  a  body  crystallizing  from  alcohol 
in  long,  brilliant,  3-ellow  needles,  melting  at  114°  and  dissolving 
gradually  in  boiling  potash  with  an  intensely  purple  colour. 

The  Aloin  of  Barbadoes  Aloes.  Dr.  E.  Schmidt.  (Abstracted 
from  the  Archiv  der  Pharmacie,  v..  No.  6,  1876  ;  Pharm.  Journ.,  3rd 
series,  vii.,  70.)  Of  the  difierent  processess  which  have  been  recom- 
mended for  the  preparation  of  aloin,  the  method  proposed  by  Tilden 
(Year-Book  of  Pharmacy,  1870)  was  found  to  give  the  most  satis- 
factory results.  According  to  this  method,  the  aloes  crushed  small 
is  dissolved  in  nine  or  ten  times  its  weight  of  boiling  water  acidified 
with  sulphuric  acid.  After  cooling  and  standing  for  a  few  hours, 
the  clear  liquid  is  decanted  from  the  resin,  and  evaporated.  The 
concentrated  solution  deposits  a  mass  of  yellow  crystals,  which  can 
be  purified  by  washing,  pressure,  and  recrystallization  from  hot 
spirit.  After  several  recrystallizations  the  aloiri  is  obtained  in  the 
form  of  beautiful  yellow  needles,  which  are  pretty  soluble  in  water 
and  in  alcohol,  but  .soluble  with  difficulty  in  ether. 

The  melting  point  was  found  to  vary,  according  as  the  crystals 


rHARMACEUTICAL    CHEMISTRY.  oU 

contain  Wcafcer  or  not.  The  crystals  melt  between  70°  and  80°,  and 
the  anhydrous  sJubstance  at  146°-148°  (Stenhouse  150°). 

Aloin  contains  water  of  crystallization  which  it  loses  completely 
when  left  over  sulphuric  acid,  or  when  dried  at  100°.  The  quantity 
of  water  present,  however,  is  by  no  means  constant ;  for  not  only 
do  different  preparations  differ  from  one  another,  but  even  the  same 
material,  according  to  the  concentration  and  temperature  of  the 
solution,  from  which  it  is  deposited. 

The  air-dried  substance  heated  to  100°  lost  in  three  experi- 
ments,— 

I.  II.  HI. 

5-89  6-77  7-01  per  cent,  of  water. 

Another  product  lost  under  similar  circumstances, — 

IV. 
11-93  per  cent,  of  water. 

In  anotber  case  the  first  crop  of  crystals  dried  in  the  air,  then  at 
100°  lost,— 

V.  ,    VI.  VII.  VIII. 

11-56  11-89  11-79  11-60; 

whilst  a  subsequent  deposit  of  crystals  gave  the  following  percent- 
ages : — 

IX.  X.  XI.  XII.  XIII. 

13-76  14-04  14-29  13-90  14-01 

Some  aloin  exposed  for  a  long  time  over  sulphuric  acid  lost  13"4i 
per  cent,  of  water,  a  loss  which  was  not  increased  by  afterwards 
heating  it  to  100°. 

It  appears  from  these  results  tbat  aloin  is  capable  of  uniting  with 
water  of  crystallization  in  several  proportions,  which  depend  upon 
the  temperature  and  state  of  concentration  of  the  solution  from 
whicb  it  is  obtained. 

According  to  the  formula  C^^  H^g  0^ — 

Oue  moleciile  of  water  requires 
Two  molecules 
Three  molecules 

With  the  formula  C^g  H^g  Oy — 

One  molecule  of  water  requires 
Two  molecules 
Three  molecules     . 

It  seems,  therefore,  that  aloin  may  crystallize  with  either  one,  two,  or 
three  molecules  of  water. 


5-52 

per 

cent. 

10-46 

,, 

14-91 

i» 

5-29 

per 

cent. 

10-11 

,, 

14-44 

,, 

40  YEAR-BOOK   OF    PHARMACY. 

This  vamtion  of  the  water  agrees  with  the  observations  of  Fliick- 
iger  upon  the  aloin  of  Zanzibar  aloes,  a  substance  which,  accord- 
ing to  Tildeu,  is  isomeric  with  the  aloin  of  Barbadoes. 

Liebelt  made  numerous  combustions  of  the  aloin  dried  at  100°, 
and  the  percentages  of  carbon  and  hydrogen  obtained  by  him  are  as 
follows  : — 


I. 

II. 

IIT. 

rv. 

c 

58-C8 

58-30 

58-41 

58-33 

H 

5-73 

5-71 

5-71 

5-47 

V. 

VI. 

vn. 

viir. 

C 

58-42 

58-48 

58-17 

48-66 

H 

5-57 

5-70 

5-33 

5-23 

IX. 

X. 

XI. 

Mean. 

C 

58-66 

58-33 

58-71 

58-46 

H 

5-81 

5-84 

5-69 

5-61 

With  these  data  there  is  a  choice  between  two  empirical  formulaj : 
0^5  Hjg  0-,  which  requires — 

C     58-44 
H      5-50, 

and  0^5  Hj7  0^,  for  which  the  percentages  must  be  — 

C    58-25 
H      5-50. 

Various  considerations  seem  to  indicate  that  the  former  of  these 
two  expressions  should  be  adopted,  especially  as  Von  Sommaruga 
and  Egger  had  obtained  similar  results  with  the  aloin  of  Socotime 
aloes. 

Nevertheless  this  formula  cannot  be  accepted.  Soon  after  the 
publication  of  Liebelt's  analytical  results  in  the  Berichte  der 
deutsch.  Ges.  zu  Berlin  (November,  1875),  the  author  became  ac- 
quainted with  the  paper  read  by  Dr.  Tilden  before  the  British 
Pharmaceutical  Conference  in  August,  1875.  In  that  paper  the 
formula  C^q  Hjg  Oy  is  proposed,  on  the  basis  of  analytical  results 
obtained  with  the  aloin  and  with  its  chloro,  bromo,  and  acetyl  substi- 
tution derivatives.  These  results  led  the  author  to  recrystallize  tlie 
aloin  in  his  possession,  and  to  submit  it  again  to  analysis,  this  time 
drying  it  in  a  vacuum.  The  results  showed  that  Liebelt's  analyses 
had  furnished  somewhat  too  little  carbon.  The  following  numbers 
were  obtained  : — 


Mean. 

1. 

n. 

in. 

IV. 

(Schmidt). 

c 

59-31 

59-45 

58-96 

59-19 

59-23 

H 

5-39 

5-63 

6-08 

5-34 

5-61 

PHARMACEUTICAL    CHEMISTKY.  41 

The  formula  C^q  H^g  0^  requires — 

C     59G2  per  cent. 
H      559 

This  formula,  therefore,  seems  to  be  established. 

The  author's  results  with  the  bromo  and  chloro  derivatives,  how- 
ever, do  not  entirely  agree  with  those  described  by  Tilden.  Wben 
an  aqueous  solution  of  aloin  is  mixed  with  excess  of  bromine  water, 
a  copious  yellow  precipitate  is  obtained,  as  long  ago  shown  by 
Stenhouse.  This  yellow  precipitate,  dried  and  crystallized  from 
alcohol,  yields  beautiful  yellow  needles.  This  compound,  however,  is 
not  a  homogeneous  substance,  for  it  seems  to  contain  not  only  tri- 
bromaloin,  which  is  the  chief  product,  but  also  small  quantities  of 
compounds  richer  as  well  as  poorer  in  bromine,  which  are  very 
difficult  to  separate  on  account  of  their  almost  equal  solubility. 
Although  several  preparations  were  made,  especially  by  the  intro- 
duction of  aloin  solution  into  excess  of  bromine  water,  and  the  com- 
position of  these  specimens  was  not  altered  by  repeated  crystalliza- 
tion, the  analytical  results  were  found  to  agree  sometimes  with  the 

TT  TT 

formula  C.-  -p,^^  O7,  sometimes  with  the  formula  C^^g  -n^"  O7. 
nv^  i^rg 

All  these  brominated  compounds  exhibit  much  greater  stability 
than  pure  aloin.  They  crystallize  readily  from  alcohol  in  golden 
needles,  which  are  almost  insoluble  in  water  and  ether.  The  melting 
point  appears  to  be  190°  to  191°.  Bromaloin  also  contains  water  of 
crystallization. 

The  air-dried  substance  lost  at  100°  the  following  quantities  per 
cent. : — 

I.  II.  III.  rv.  V. 

9-00  9-22  9-06  11-93  10-oG 

A  variation  in  the  amount  of  water  is  exhibited   here,  as  in  the  case 

TT 
of  pure  aloin.     The  formula  C^gra^'O^,  with  oHoO,  requires  881 

per  cent,  of  water  ;  with  4  H^  0  11*41  per  cent. 

The  substance  dried  at  100^  gave  when  burnt  with  chromate  of 
lead  the  following  percentages  of  carbon  and  hydrogen.  The 
bromine  was  determined  by  the  method  of  Carius  : — 


I. 

II. 

III. 

rv. 

V. 

C     33-36 

33-38 

33-49 

33-17 

33-13 

H      317 

2-76 

2-89 

2-93 

3-06 

Br  48-31 

43-38 

43-60 

43-63 

43-76 

42  YEAR-BOOK    OF    PHARMACY. 

n.  YIT.  Tin.          IX.            X.  XT. 

C     33-47  33-84  33-71  35-15  34-27  34-24 

H      2-69  2-70  3-02        2-97        3-11  2-01 

Br   43-47  4322  —  41-44  43-08  — 

The  following  percentages  ai'e  required  for  the  two  formuloe  re- 
ferred to  : — 

C.sH^Br.O,  C,„H,5Br,0, 

C    33-08 34-34 

H      2-39 .       2-68 

Br  44-03 42-93 

The  author  has  not  been  successful  in  pi'oducing  from  aloin  a 
definite  chlorinated  product  by  the  action  of  chlorine  either  in  the 
gaseous  form  or  in  aqueous  solution.  But  by  the  action  of  potassic 
chlorate  and  hydi-ochloric  acid,  according  to  Tilden's  process,  a 
yellow  substance  was  obtained  which  crystallizes  in  beautiful 
needles.  The  analysis  of  this  compound,  however,  led  to  numbers 
which  vary  still  more  than  those  obtained  in  the  analysis  of  the 
corresponding  brominated  derivative.  The  percentages  of  chlorine 
obtained  were  as  follows  : — 

I.  II.  III.  IV.  V. 

23-02  24-47  25-67  25-55  26-83 

The  formula  C^g  H^j  CI3  0-  requires  2r)'03  per  cent. 

The  author  finds  that  barbaloin  when  digested  with  nitric  acid 
yields  chrysammic,  picric,  oxalic,  and  carbonic  acids. 

The  action  of  zinc  dust  when  heated  with  aloin  has  already  been 
observed  by  Graebe  and  Liebermann,  who  obtained  a  hydrocarbon 
which  they  believed  to  be  anthracene.  As,  however,  it  is  not  clear 
which  kind  of  aloin  these  chemists  operated  upon,  the  author  has 
repeated  the  experiment  with  Barbadoes  aloin,  and  finds  that  the 
hydrocarbon  derived  from  this  source  is  principally  methyl-anthra- 
cene. 

The  melting  point  was  210°-212°.  By  oxidation  with  chromic 
acid  dis.solved  in  acetic  acid  it  furnished  anthracene  mono-carbonic 
acid  (melting  point  281°)  soluble  in  ammonia,  also  a  small  quantity 
of  a  body  having  the  properties  of  anthraquinone.  The  melting 
point  of  this  latter  was,  however,  not  constant  (210°  to  240°);  and 
it  may,  therefore,  be  assumed  that  it  consisted  of  a  mixture  of 
anthraquinone  and  methyl-anthraquinone.  Whether  this  anthra- 
quinone is  a  product  of  the  decomposition  of  methyl-anthracene,  or 
is  formed  by  the  direct  oxidation  of  a  small  quantity  of  anthracene, 
cannot  be  at  present  determined.     The  quantity  of  methyi-anthra- 


i 


PHARMACEUTICAL    CHEMISTUY.  43 

cene  obtainable  from  barbaloin  is  exceedingly  small  (about  1  part 
of  the  hydrocarbon  from  200  of  the  'aloin) ;  so  that  the  aloin  can 
scarcely  be  regarded  as  a  dii'ect  derivative  of  methyl-anthracene. 

The  Camphor  of  Inula  Helenium.  J.  Kallen.  {Ber.der  deutscli. 
Chem.-Ge^.,  ix.,  IS-i-lo?.)  The  author  has  continued  his  researches 
on  this  subject.  The  inula  camphor  was  obtained  in  the  form  of 
white  crystals  by  distilling  elecampane  root  with  steam.  On  press- 
ing the  crystals  between  bibulous  paper,  and  distilling  the  latter  with 
water,  a  yellowish  liquid,  alantol,  is  obtained,  having  an  aromatic 
taste  and  the  odour  of  peppermint,  and  boiling  near  200°  C.  Its 
composition  is  C^^qH^qO. 

The  crystals  remaining  after  pressing  are  repeatedly  crystallized 
from  dilute  alcohol,  when  they  form  colourless  prismatic  needles,  of 
a  faint  odour  and  taste,  fusing  at  66°  C,  and  sublimate  ;  readily 
soluble  in  alcohol  and  ether,  but  slightly  in  water.  It  is  the  anhy- 
drid  of  a  new  acid  (alantsaure),  of  the  formula  C]^^  Hjq  Oj  ;  the  acid 
is  Ci5  Ho2  Og,  crystallizes  in  fine  needles,  fuses  at  90°-91°  C,  and 
yields  i-ather  unstable  crystallizable  salts. 

Tannin  as  a  Test  for  the  Purity  of  Water.  H.  Kammerer. 
(Journ.  filr  Pract.-Ghem.,  1876,  322.)  The  application  of  tannin  is 
recommended  by  the  author  for  the  detection  of  albuminoid  and 
other  animal  organic  matter  in  water.  Any  sample  of  water  form- 
ing a  precipitate  or  turbidity  with  a  solution  of  tannin  should  be 
condemned  as  unfit  for  drinking.  As  some  saline  constituents  of 
potable  waters  retard  the  precipitation  of  organic  impurities  by 
tannin,  the  mixture  should  be  allowed  to  stand  for  twenty-four 
hours  before  a  negative  result  is  to  be  regarded  as  an  indication  of 
purity. 

Creasote  and  Carbolic  Acid.  A.  Griitzel.  (Archiv  der  Pharm., 
Feb.,  1877;  New  Beinedies,'Meij,  1877.)  Pure  beechwood-tar  creasote 
must  have  the  following  properties  : — It  is  a  colourless,  at  most 
light  straw  yellow  oily  liquid  of  sp.  gr.  I'OSO,  distilling  unaltered 
between  200°-225°  C.  Exposure  to  light  and  air,  even  for  months, 
should  impart  to  it  at  most  only  a  dark  wine  yellow,  but  never  a  red 
colour,  which  would  be  indicative  of  foreign  matters.  It  must  be 
entirely  soluble  in  caustic  alkali,  and  on  adding  water  no  oily 
hydi'ocarbons  must  be  set  free.  These  latter,  if  present,  are  very 
difficultly  removable,  and  possess  a  very  disagreeable  odour.  It  is 
soluble  in  80  parts  of  cold  water,  and  in  less  of  boiling  water,  but 
the  excess  separates  on  cooling.  It  is  miscible  with  50  per  cent,  of 
its  volume  of  glycerin  of  sp.  gr.  1'250. 


44  year-book  of  pharmacy. 

Reactions  of  Creasotes  and  Carbolic  Acids. 

A.     Li  Aqiieoiis  Solution. 
To  15  ili-ops  of  the  solution  to  be  tested  is  added  1  drop  of  the  reagent. 


Reagents. 


Beechwood-Tar  Crea- 
sote. 


Carbolic  Acui. 


Ferric         chloride  j  Blue  on  first  con-  I  Permanently 
(cryst.),  dissolved       tact,  then  brown  ;       violet. 
in  10  parts  water. 


On  further  addition 
of  same. 

Ferric  acetate,  dry, 
in  10  parts  of 
water. 


Ferric  sulphate, 
dry,  in  20  parts  of 
water. 


Plumbic  nitrate  in 
10  parts  of  water. 


Stannous  chloride 
in  10  parts  water. 


Plumbic  acetate, 
neutral, in  lOparts 
water. 


tact,  then  brown ; 
on  standing, 

orange. 

Dark  brown  i^re- 
cipitate. 

Brown,  then  with  a 
shade  of  violet ; 
lastly  brown  pre- 
cipitate. 

Blue,  then  with  a 
shade  of  violet ; 
lastly  brown 

precipitate. 

Clear ;  no  reac- 
tion. 


"White  precipitate, 
soluble  in  excess 
of  reagent. 

"WTiite  precipitate, 
soluble  in  excess. 


Permanently 
violet. 

Brown  and  clear 
solution. 


Permanently 
violet. 


Opalescence ;  on 
standing,  small 
deposit. 

Small  precipitate, 
insoluble  in  ex- 
cess of  reagent. 

Small  precipi- 
tate, soluble  in 
excess. 


English  Creasote. 


Blue  on  first  con- 
tact, then  olive 
green ;  finally 
dirty  yellow. 

Light  brown  pre- 
ciijitate. 

Brown  and  clear 
solution. 


Grass  green  on 
first  contact ; 
then  yellow  pre- 
cii^itate. 

Opalescence ;  on 
stantling,  small 
deposit. 

Small  precipitate, 
insoluble  in  ex- 
cess of  reagent. 

White  precipitate, 
only  partially  so- 
luble in  excess. 


B.     1  Part  Dissolved  in  10  Parts  of  92  pe7' cent.  Alcohol. 


Aqueous  solution 
of  ferric  chloride 
with  one  drop  of 
alcoholic  solution. 


Blue  on  first  con- 
tact, then  green. 


Violet  on  first 
contact,  then 
green. 


Green  on  first  con- 
tact, then  fine 
azure  blue. 


C.     Carbolic  Acid  and  Creasotes  unmixed  loith  any  Solvents. 


Saturated  alcoholic 
ferric  solution 
with   one    drop. 

With  several  drops. 


Dirty  violet. 


At  once  green. 


Greenish  yellow 
on  first  contact, 
then  brown. 

At  once  green. 


Green  on  first  con- 
tact, then  a  light 
mud  brown. 

At  once  green. 


PHARMACEUTICAL    CHEMISTRY.  45 

Decomposition  of  Ammonium  Salts  in  Aqueous  Solutions  by- 
Salts  of  Potassium  and  Sodium.  Dr.  H.  C.  Dibbits.  {Zuitschr. 
far  Anah/t.-Chein.,  1S7G,  245.)  In  a  previous  report  (see  Year-Book 
of  rharmacy,  1876,  112)  the  author  has  shown  that  aqueous  solu- 
tions of  the  crystallized  salts  of  ammonium  part  with  ammonia  upon 
boiling,  and  that  the  quantity  of  ammonia  thus  liberated  varies  con- 
siderably with  the  different  ammonium  compounds.  He  has  now 
examined  this  behaviour  of  ammonium  salts  in  solutions  containing 
also  various  quantities  of  a  potassium  or  sodium  salt,  in  order  to  solve 
the  problem  whether  or  not  a  mutual  decomposition  takes  place 
between  the  two.  By  dissolving,  for  instance,  equivalent  propor- 
tions of  ammonium  sulphate  and  potassium  chloride,  and  determin- 
ing the  loss  of  ammonia  during  the  boiling  of  this  solution,  he  wished 
to  ascertain  whether  this  loss  is  equal  to  that  occurring  vpith  am- 
monium sulphate,  or  to  that  occurring  -with  ammonium  chloride ; 
or  in  other  words,  whether  the  two  salts  introduced  continue  to 
exist  as  such,  in  the  boiling  solution,  or  whether  they  form  am- 
monium chloride  and  potassium  sulphate.  The  results  prove  that 
a  decomposition  takes  place,  but  only  a  partial  one  ;  so  that  in 
the  instance  named,  the  boiling  solution  contains  four  salts,  viz., 
ammonium  chloride,  ammonium  sulphate,  potassium  chloride, 
and  potassium  sulphate.  The  salts  experimented  with  were  the 
sulphate,  oxalate,  and  acetate  of  ammonium  on  the  one  hand,  and 
the  chlorides  and  nitrates  of  potassium  and  sodium  on  the  other. 
The  mutual  decomposition  increases  with  the  quantity  of  chloride 
or  nitrate  (of  K  or  Na)  employed,  but  is  never  complete.  In  every 
case  the  boiling  solution  was  found  to  contain  four  salts. 

The  Detection  and  Quantitative  Determination  of  Free  Sulphuric 
and  Hydrochloric  Acids  in  Vinegar,  Lime  and  Lemon  Juices,  and 
Similar  Liquids.  0.  Hehner.  (From  the  Analyst.)  As  vinegar 
consists,  except  in  the  case  of  its  being  distilled,  not  merely  of  acetic 
acid  and  water,  but  always  contains  acetates  or  tartrates  of  potash 
and  soda  and  chloride  of  sodium,  it  is  obvious  that  sulphuric  or  hydro- 
chloric acid,  if  added  in  small  quantity,  can  no  longer  be  considered 
to  exist  as  such  in  vinegar,  but  that  they  decompose  an  equivalent 
quantity  of  acetate  or  tartrate.  Whenever  there  is  any  undecomposed 
acetate  or  tartrate  present  in  vinegar,  no  trace  of  any  mineral  acid 
can  be  pi'esent  in  the  free  state.  As  the  organic  salts  of  the  alkalies 
are  converted  by  incineration  into  the  corresponding  carbonates,  it 
can  safely  be  asserted  that  -whenever  the  ash  of  a  vinegar  exhibits  an 
alkaline  reaction,  free  mineral  acid  cannot  be  present  in  the  vinegar. 
A  trace  of  mineral  acid  may  have  been  added,  but  it  then  has  become 


46  TEAR-BOOK    OF    PHARMACY. 

neutralized  by  the  decomposition  of  the  acetates  or  tartrates.  We 
have  thus  the  simplest  possible  qualitative  test  for  free  mineral 
acids  in  vinegar. 

But  whenever  the  ash  is  neutral,  free  mineral  acid  is  most  likely 
present.  The  quantity  of  this  may  be  ascertained  with  accuracy  by 
following  the  same  principle.  The  process  is  as  follows  : — 50  c.c.  of 
the  vinegar  are  mixed  with  25  c.c.  of  decinormal  soda  solution,  or 
with  a  sufficient  quantity  so  that  on  evaporation  and  incineration 
;m  ash  having  an  alkaline  reaction  is  left ;  the  residue  is  dissolved 
in  decinormal  sulphuric  acid  corresponding  to  the  soda  solution, 
boiled  to  expel  carbonic  acid,  filtered,  the  filter  washed  with  water, 
the  liquid  reddened  by  litmus  and  neutralized  by  decinormal  soda 
solution,  the  volume  of  which  indicates  directly  the  proportion  of 
free  mineral  acid  present, — 100  cc.  of  the  standard  solution  corre- 
sponding to  0*49  gram  of  Ho  S  0^^. 

The  same  process  is  likewise  applicable  for  the  determination  of 
free  mineral  acid  in  lime  and  lemon  juice. 

A  Method  of  Detecting  and  Estimating  Castor  and  other  Fixed 
Oils  in  Copaiba.  Dr.  Muter.  (  From  a  paper  read  before  the  Society 
of  Public  Analysts,  November  15th,  1876  ;  the  Analyst,  November 
30th,  1S76.)  Observing  the  close  affinity  between  copaivic  and 
pinic  acids,  the,  author  suggests  a  process  of  analysis  based  upon 
the  difference  of  solubility  of  the  sodium  soaps  in  a  mixture  of  ether 
and  alcohol.  A  mixture  of  five  volumes  of  absolute  ether  and  one 
volume  of  absolute  alcohol  has  been  recommended  as  a  very  good 
solvent  for  sodium  pinate  by  M.  Barfocd,  who  states  that  sodium 
oleate  is  soluble  in  this  menstruum  only  to  the  extent  of  1  in  1000 
(calculated  for  oleic  acid). 

The  process  employed  by  Dr.  Muter  is  as  follows  : — 3  to  4  grams 
of  the  sample  are  weighed  into  a  clean  di-y  flask,  and  saponified  on 
the  water  bath  with  50  c.c.  of  alcohol  and  a  lump  of  caustic  soda, 
weighing  not  less  than  5  grams.  When  all  is  dissolved  water  is 
added,  and  the  whole  washed  into  a  half-pint  basin  so  as  to  nearly 
fill  it,  and  evaporated  to  lOO  c.c.  over  a  low  gas  flame.  Dilute  sul- 
phuric acid  is  then  added  till  the  whole  just  becomes  permanently 
turbid,  and  then  solution  of  caustic  soda  is  dropped  in  till  it  just 
clears  again.  By  this  m.eans  a  solution  is  obtained  with  the  least 
possible  excess  of  alkali,  and  with  a  good  amount  of  sodium  sulphate. 
The  whole  is  now  evaporated  to  perfect  dryness  on  the  water  bath, 
stirring  towards  the  end,  so  that  the  sulphate  may  mix  with  the 
soaps  and  produce  an  easily  pulverulent  residue.  The  residue 
is  removed  from  the  basin  into  a  small,  wide  mouthed,  stoppered 


PHARMACEUTICAL   CHEMISTRY.  47 

bottle,  treated  with  70  e.c.  of  ether-alcohol,  and  well  shaken  up.  As 
soon  as  it  is  fairly  settled,  the  fluid  is  filtered  off  through  a  quick 
filter;  and  this  is  repeated  with  two  successive  quantities  of  70  c.c, 
making  210  c.c.  in  all  of  the  solvent  used.  The  residue  in  the  bottle 
and  on  the  filter  now  consists  of  sodium  oleate  and  sulphate  if  the 
balsam  be  impure,  and  of  the  latter  only  if  pure,  with  a  little  trace 
of  the  insoluble  resin  soap  already  referred  to.  The  contents  of 
the  bottle  and  filter  are  then  dissolved  in  warm  water,  and  after 
heating  until  all  smell  of  ether  is  gone,  the  whole  is  boiled,  freely 
acidulated  with  hydrochloric  acid,  and  set  to  cool.  If,  when  cold, 
nothing  but  a  few  specks  of  brown  resin  should  rise  to  the  surface, 
the  balsam  is  pure  ;  but  if  an  oily  layer  be  formed,  it  is  adulter- 
ated, and  the  smell  of  the  separated  oleic  acid  will  at  once  deter- 
mine whether  it  is  actually  castor  oil  or  not.  In  the  case  of  the 
presence  of  oil,  two  grams  of  pure  and  dry  white  wax  are  added, 
and  the  whole  heated  till  the  wax  melts  with  the  oleic  acid.  On 
cooling,  a  solid  cake  is  formed,  which  is  detached  from  the  side  of 
the  beaker,  and  the  fluid  below  passed  through  a  filter.  The  cake 
is  once  more  melted  in  boiling  water,  cooled,  detached,  dried  by 
gentle  pressure  in  blotting  paper,  put  into  the  water  oven  in  a 
weighed  platinum  dish  till  dry,  and  then  weighed,  and  the  weight 
of  the  wax  used  deducted.  The  beaker,  filter,  rod,  etc.,  used  are 
if  at  all  dirty  dried,  extracted  with  ether,  and  the  residue  left  after 
evaporation  weighed  and  added  to  the  total. 

The  calculation  is  then  performed  as  follows  : — 

1.  To  the  weight  in  grams  found,  add  "20  for  loss  of  oleic  acid  in 
solvent,  and  then  say  as  95  :  100  :  :  total  oleic  acid. 

2.  Calculate  the  percentage  from  the  quantity  taken,  and  from 
this  deduct  six  per  cent,  for  possible  altered  resin  in  the  balsam. 
The  error,  owing  to  the  correction,  of  course  increases  with  the 
amount  of  oil  present ;  but  it  is  stated  to  be  always  an  error  in 
the  direction  of  under-estimation,  which  is  the  great  point  for 
public  analysts.  When  working  on  three  to  four  grams,  with  an 
admixture  of  not  over  25  per  cent.,  the  errors  due  to  loss  of  oleic 
acid  and  insoluble  resin  soap  are  said  to  so  nearly  balance  each 
other  that  any  correction  is  unnecessary,  and  the  actual  amount  of 
oleic  acid  found  may  be  taken  as  correct  within  a  per  cent. 

The  Oil  of  Orris  Root.  Prof.  F.  A.  Fliickiger.  {Abstract  of 
a  paper  in  the  Arcliiv  tier  Pharmacie,  June,  1876  ;  Pharm.  Joiirn.,  3rd 
series,  vii.,  130.)  Orris  root  owes  its  use  during  more  than  two  thou- 
sand years  chiefly  to  its  fragrance,  which  curiously  enough  does  not 
belong  to  the  living  root.     Its  slight  and  by  no  means  aromatic 


48  TEAR-BOOK    OF    THARMACY. 

smell  is  first  developed  into  the  agreeable  perfume  after  drying,  with- 
out doubt  in  consequence  of  changes  of  a  chemical  nature,  concerning 
which  at  present  our  knowledge  is  deficient.  When  the  dried  root- 
stock  is  submitted  to  distillation  with  water,  eventually  there  appears 
upon  the  water  a  crystalline,  odorous  matter  which  is  justly  prized  in 
perfumery  and  is  specially  prepared  by  some  of  the  larger  distillers. 
But  the  yield  is  very  small,  only  about  1  part  per  1000  of  the  orris 
root  used.  The  product  is  of  a  yellowish  brown  colour,  of  the  con- 
sistency of  a  firm  ointment,  and  possesses  the  characteristic  odour  of 
orris  root. 

Oil  of  oitIs  has  hitherto  been  studied  by  H.  A.  Vogel,  and  by 
Dumas.  The  latter  in  1835  assigned  to  it  the  formula  Cg  Hg  0  (Cg 
HjgO  according  to  the  modern  notation). 

By  repeated  recrystallizations  from  alcohol  of  a  specimen  of  oil 
of  orris  prepared  by  Messrs.  Herring  &  Co.,  the  author  obtained  it, 
with  the  help  of  animal  charcoal,  in  colourless  crystalline  scales,  the 
form  of  which  could  not  be  decided.  By  this  purification  of  the  oil, 
or  presumed  stearoptene,  the  odour  was  concentrated  in  the  mother- 
liquid,  the  crystals  becoming  more  and  more  odourless,  until  finally 
they  perfectly  lost  all  aroma.  An  alcoholic  solution  of  the  crystals 
possessed  no  rotatory  power,  and  enei'getically  reddened  litmus  paper 
ruoistened  with  alcohol.  After  repeated  recrystallizations  the  melting 
point  reached  5!2°  C. ;  a  less  pure  preparation  melted  at  some  degrees 
lower  temperature.  Carbon  bisulphide  appears  to  be  unsuitable  for 
the  removal  of  the  perfume  from  orris  root ;  the  quantity  of  essential 
oil  is  exceedingly  small,  and  this  solvent  removes  with  it  a  very  soft 
resin,  tannin,  and  probably  also  fatty  matter. 

The  numbers  obtained  in  the  combustion  of  the  crystals,  viz., 
C  =  7396,  H  =  1226,  taken  in  conjunction  with  the  previous  obser- 
vations, leave  no  doubt  as  to  the  nature  of  the  presumed  orris  stear- 
optene :  it  is  myristic  acid,  C-^  H^g  0^. 

After  this  point  had  been  established  it  was  easy  to  remove  the  fat 
acid  from  the  crude  product  by  digesting  the  alcoholic  solution  with 
anhydrous  sodium  carbonate  or  bicarbonate,  and  thus  obtaining  a  soap 
solution  from  which  the  myri.stic  acid  is  precipitated  upon  addition  of 
a  stronger  acid  and  dilution  with  water.  Upon  heating  the  liquid  to 
60°  C.  it  rises  as  an  oily  layer,  which  solidifies  in  a  crystalline  form 
at  a  temperature  some  degrees  below  50°  C.  By  repetition  of  this 
treatment  the  product  may  be  easily  brought  to  approximate  and 
finally  to  attain  the  melting  point  of  pure  myristic  acid,  54°  C.  The 
effect  of  the  presence  of  the  smallest  quantity  of  the  obstinately  ad- 
hering volatile  oil,  or  of  a  trace  of  lauric  acid  (CjjHo^Oo),  melting 


PHARMACEUTICAL    CHEMISTRY.  49 

at  about  44"  C,  which  may  easily  accompany  the  myristic  acid,  must 
be  to  lower  the  melting  point. 

The  above  observations  upon  the  London  oil  were  so  far  repeated 
with  a  sample  of  oil  from  Messrs.  Schimmel  &  Co.,  of  Leipzig,  as 
was  necessary  to  show  the  identity  of  the  perfumes. 

After  these  experiments  upon  the  perfectly  odourless  myristic 
acid,  the  preparation  remains  saturated  with  a  somewhat  volatile  oil. 
Upon  digesting  the  crude  product  in  a  closed  flask  with  lead  oxide, 
the  oil  separates  as  a  rather  thick  brownish  fluid,  which  remains 
fluid  at  10°  C. 

As  the  oil  containing  myristic  acid  is  only  obtained  by  tlie 
most  careful  distillation,  in  the  proportion  of  about  1  in  1000,  the 
quantity  occurring  in  the  root  itself  may  be  estimated  as  being  much 
smaller  still,  possibly  not  amounting  to  1  in  10,000.  It  may  pro- 
bably be  included  in  the  as  yet  uninvestigated  class  of  so-called  fer- 
ment oils,  in  that  so  far  as  is  indicated  by  the  smell  it  does  not  occur 
in  the  living  root.  The  question  arises,  how  the  myristic  acid,  which 
can  only  with  difficulty  be  distilled  without  decomposition,  passes 
over  with  the  oil.  The  explanation  of  this  is  to  be  sought  in  the 
phenomenon  of  difl'usion.  Rose  oil  is  similarly  accompanied  by  a 
stearoptene  that  it  is  difficult  to  volatilize  by  itself. 

The  occurrence  of  myristic  acid  in  oil  of  orris  is  probably  to  be 
attributed  to  a  fat  which  is  present  in  the  root,  and  is  split  up  by 
the  vapour  of  water.  The  quantity  of  this  fat  must  be  very  small, 
since  300  grams  of  orris  root  powder  exhausted  with  carbon  bisul- 
phide gave  a  soft  perfumed  resin,  but  neither  free  myristic  acid  nor 
neutral  fat  could  be  detected.  The  author  also  sought  to  ascertain 
whether  free  myristic  acid  was  already  present  in  the  root.  The 
carbon  bisulphide  extract  was  digested  with  sodium  carbonate  and 
alcohol,  in  order  to  obtain  a  solution  of  sodium  resinate  and  myris- 
tate,  from  which  the  acid  sought  could  be  precipitated  by  acetic  acid. 
If  myristic  acid  were  present,  it  would  on  prolonged  digestion  of 
the  turbid  acid  liquid  gradually  rise  to  the  top  as  an  oily  layer.  This, 
however,  did  not  take  place  even  after  several  days  ;  the  brown 
resinate  slowly  sank  to  the  bottom  as  a  pulverulent  mass,  and  the 
liquid  became  clear  without  yielding  an  oily  layer. 

Alkaliinetric  Titration  of  Magnesia,  Phosphoric  Acid,  and 
Arsenic  Acid.  Prof.  F.  Stolba.  (Ber.  der  Bohm.-Ges.  cler  Wis- 
sensch.,  1876,  v.)  Magnesia,  as  well  as  phosphoric  and  arsenic  acids, 
are  frequently  estimated  by  precipitation  as  phosphate  or  arseniate 
of  ammonium  and  magnesium,  and  weighing  the  arseniat^  as  such 
and  the  phosphate  after  iguition   as  pyrophosphate  of  magnesium. 

E 


50 


YEAR-BOOK    OF    PHARMACY. 


In  the  place  of  this  gravimetric  process,  the  author  recommends  a 
volumetric  one,  requiring  less  time. 

Freshly  precipitated  and  properly  washed  phosphate,  or  arseniate 
of  ammonium  and  magnesium,  when  suspended  in  water,  imparts 
to  the  latter  an  alkaline  reaction,  as  may  be  seen  by  the  violet 
coloration  produced  on  the  addition  of  a  few  drops  of  tincture  of 
cochineal.  The  degree  of  alkalinity  maybe  determined  by  standard 
hydrochloric  or  sulphuric  acid,  as  will  be  seen  from  the  following 
equations  : — 

Mg.  N  H^.  P  0^  +  2  H  CI  -  N  H^  H..  P  O.^  +  Mg  Clo ; 
Mg.  N  H^.  As  O4  +  2  H  CI  =  N  H^  H..  As  O4  +  Mg  Clg. 
As  1  c.c.  of  normal  acid  thus  corresponds  to 
0-020    gram  of  Mg  0, 
0-0355     „      „  PjOj,  and 
0-0575     „      „  AS2O5, 

the  author  recommends  the  application  of  deci-normal  acid,  especi- 
ally as  the  reaction  with  carmine  is  sufficiently  delicate  for  this 
purpose.  Tincture  of  brazil  wood  can  also  be  used  as  an  indicator. 
The  modus  operandi  is  as  follows  : — 

The  precipitate,  after  being  well  washed  with  solution  of  ammonia 
and  then  with  rectified  spirit,  until  the  alcoholic  washings  cease  to 
be  alkaline,  is  introduced,  together  with  the  filter,  into  a  flask  con- 
taining 100-200  c.c.  of  hot  water,  and  well  mixed  with  the  latter  by 
means  of  a  glass  rod  or  thick  platinum  wire.  Decinormal  hydro- 
chloric acid  is  now  slowly  added  from  a  burette  in  moderate  excess, 
the  mixture  being  continually  stirred  during  the  addition,  and  the 
excess  of  acid  titrated  with  decinormal  Ka  H  0.  The  results  are 
stated  to  be  very  satisfactory. 

From  a  solution  containing  calcium  as  well  as  magnesium,  the 
former  is  first  precipitated  by  oxalate  of  ammonium  in  the  presence 
of  chloride  of  ammonium,  and  then  the  magnesium  by  phosphate  of 
sodium  and  hydrate  of  ammonium,  without  previously  removing 
the  calcium  precipitate  by  filtration.  As  the  presence  of  oxalate  of 
calcium  does  not  interfere  with  the  process,  the  mixed  precipitates 
are  treated  in  the  same  manner  as  already  described. 

Po.«sib]y  lithium  may  be  estimated  by  the  same  method. 

Preparation  of  Platinum  Black  by  means  of  Glycerin.  R. 
Zdrawkowitch.  (Bull.  Sac.  Chim.  [2],  xxv.,  ll>8.)  Platinum 
black  in  a  highly  active  condition  can  be  obtained,  according  to  the 
author,  by  adding  3  to  5  c.c.  of  solution  of  perchloride  of  platinum, 
drop  by  drop,  to  a  boiling  mixture  of  15  c.c.  of  glycerin  and  10  c.c. 
of  solution  of  caustic  potash  of  1*08  sp.  gr. 


, 


PHARMACEUTICAL    CHEMISTUY.  51 

Note  on  Carvol.  Prof.  F.  A.  Flilckiger.  (Abstract  of  a  paper 
read  before  the  Berlin  Chemical  Society  :  Pharm.  Journ.,  from  Ber. 
der  deutsch.  Chem.-Ges.,  ix.,  468.)  Volckel,  in  1840,  pointed  out  that 
oil  of  cumin  consisted  of  a  hydrocarbon  and  a  portion  containing 
oxygen,  to  which  Berzelius  afterwards  gave  the  name  of  carvol. 

This  body  was  more  minutely  examined  by  Schweizer,  in  1841. 
He  found  that  upon  treatment  with  caustic  potash,  glacial  acetic 
acid,  or  iodine,  it  undergoes  a  remarkable  change  ;  that  it  is  specially 
soluble  in  potash,  acquiring  a  very  acrid  taste,  for  which  reason 
Schweizer  designated  the  product  carvacrol.  When,  in  1842,  Claus 
prepared  camphor  creasote  by  boiling  camphor  with  iodine,  Schweizer 
at  once  recognised  its  analogy  with  carvacrol.  In  1844  he  also 
obtained  this  compound  by  similar  treatment  of  oil  of  Thuja  occlderi,- 
tcdis.  Since  then  the  methods  of  obtaining  this  body — at  present 
looked  upon  as  oxycymol,  but  probably  more  correctly  oxycymene 
— have  been  multiplied.  Pott  obtained  it  by  melting  potassium 
cymensulphonate  with  potassium  hydrate,  the  cymene  employed 
being  prepared  by  the  action  of  phosphorsulphide  upon  camphor. 
H.  Miiller  melted  caustic  soda  with  sodium  cymensulphonate  with 
the  same  result,  the  cymene  (cymol)  having  been  obtained  from  the 
oil  of  ajowan  fruit  (Amini  copticum,  L.  =  PtycJwsis  ajotaan  and  P. 
coptica,  D.  C).  It  now  appears  probable  that  cymene  can  be  obtained 
by  suitable  treatment  from  any  of  the  essential  oils  having  the  com- 
position CjQ  Hjg,  as  well  as  from  many,  if  not  all,  that  differ,  by  the 
addition  of  O  or  0  Hg,  and  the  chemical  identity  of  cymene  from 
the  most  diverse  sources  may  now  be  accepted ;  but  the  optical  pro- 
perties of  this  substance  have  hitherto  only  attracted  the  attention 
of  Schiff  and  Guareschi.  It  remained  to  be  seen  whether  cymene 
from  other  sources  possessed,  for  instance,  the  same  rotatory  property 
as  that  prepared  from  cumin  oil  by  Guareschi.  The  author  thinks 
that  this  property  will  generally  be  found  wanting  in  artificial 
cymenes,  whether  prepared  synthetically  or  by  reduction  of  C^q  H^g, 
Cjo  Hjg  0,  or  C^o  His  O-  Probably  oxycymene  is  always  without 
optic  action ;  carvacrol  prepared  by  the  author  from  oil  of  cumin 
being  without  rotatory  power.  The  author  points  out  that  oxycy- 
mene differs  from  carvol  in  being  permanently  coloured  green  by 
alcoholic  perchloride  of  iron,  refracting  light  strongly,  not  penetrat- 
ing the  cork  so  readily,  and  not  giving  the  creaking  noise  peculiar 
to  carvol  and  other  thin  volatile  oils  when  rubbed  against  the  side  of 
a  glass  vessel. 

Carvol  is  the  only  oil  that,  as  noticed  by  Yarrentrapp  in  1849, 
combines  directly  with  S  Hg.     The  author  has  used  a  slight  modifica- 


OJ,  YEAE-BOOK    OF    PHARMACY. 

tion  of  Varrenfcrapp's  method  in  testing  whether  carvol  is  as  limited 
in  its  distribution  in  nature  as  the  corresponding  hydrocarbon, 
cymene  or  cymol.  The  oil  to  be  tested  is  diluted  with  one-fourth 
its  volume  of  alcohol  (sp.gr.  '830),  and  then  saturated  with  sulphu- 
retted hydrogen.  Upon  the  addition  of  only  a  little  concentrated 
ammonia,  or  better  still,  absolute  alcohol  saturated  with  ammonia, 
it  solidifies  to  a  crystalline  paste  of  carvol  sulphydrate  (C^q  ^^it  ^)-2 
S  Ho,  or  C20H3QO2  S.  Pure  carvol  is  not  necessary  to  the  obtain- 
ing of  this  product ;  it  is  yielded  by  both  the  crude  and  rectified 
cumin  oil  of  commerce.  If  the  crystallization  does  not  take  place 
immediately,  it  can  be  rapidly  induced  by  the  passage  of  a  few  bub- 
bles of  sulphuretted  hydrogen.  The  crystals  can  be  washed  with 
cold  alcohol,  and  after  further  purification  by  recrystallization,  they 
have  neither  smell  nor  taste.  They  can  be  decomposed  by  gentle 
heating  with  alcoholic  soda ;  and  upon  dilution  with  hot  water  pure 
carvol  separates. 

Carvol  from  cumin  oil  rotates  the  polarized  beam  strongly  to  the 
right,  giving  with  a  column  of  liquid  25  mm.  long,  in  a  Wild's 
polariscope,  and  with  the  sodium  light,  a  deviation  of  not  less  than 
15"6°.  The  hydrocarbon  of  cumin  oil,  carvene,  is  very  strongly 
dextrogyre,  to  the  extent  of  26'8°,  under  the  same  conditions. 

Bolley  has -stated,  that  in  distilling  oil  of  curcuma,  he  had  found 
the  portion  passing  over  beetwen  230°  and  250°  C.  to  give  the  formula 
CjQ  H|j  0,  whilst  its  behaviour  with  sulphide  of  ammonicum  pointed 
to  its  being  an  isomer  with  carvol.  The  author,  however,  failed  to 
get  from  curcuma  oil  a  product  corresponding,  either  in  boiling 
point  or  composition,  with  carvol ;  and  four  different  portions,  equally 
with  the  crude  oil,  failed  to  give  the  crystals  C.-,o  Hg^  Oo  S. 

The  author  next  examined  oil  of  myrrh,  which  according  to  Rin- 
koldt's  analysis  agi-eed  in  composition  with  carvol.  An  oil  prepared 
by  him  from  good  myrrh,  under  the  conditions  above-mentioned, 
rotated  15°  to  the  left,  and  yielded  no  sulphuretted  hydrogen  com- 
pound. Further,  its  elementary  analysis  did  not  correspond  with 
carvol.  Herr  Buri  found  in  the  crude  oil,  C  =  8470,  H  -  9*98  per 
cent. ;  and  in  the  principal  portion,  distilling  between  262°  and  263°, 
C  =  8470,  H  =  10-26.  The  formula  Co..  H30  O  would  requii-e  C  =  84-62, 
H  10-25,  0  =  513. 

Oils  of  the  composition  of  Cjq  Hj^  0  have  been  reported  with 
more  or  less  probability  as  present  in  oil  of  nutmeg  and  eucalyptus 
oil.  Gladstone  has  already  shown  that  the  elements  of  the  first 
formed  no  combination  with  oil  of  nutmeg  ;  and  this  the  author  con- 
firms, and  gives  the  same  report  of  oil  of  mace,  his  experiments 


PHARMACEUTICAL   CHEMISTRY.  53 

having  been  made  with  samples  distilled  by  himself.  Neither  did 
he  obtain  carvol  sulphydrate  from,  a  commercial  eucalyptus  oil. 

Oil  of  dill  fruit  (Anethum  graveoleiis)  yielded  to  Gladstone  a  portion 
behaving  like  the  carvol  of  cumin  oil,  and  the  chemical  identity  of 
the  two  oils  has  been  established  by  Nietzki.  The  author  finds  it 
unnecessai'y  to  separate  the  carvol,  as  the  crude  oil  gives  an  abundant 
yield  of  crystals,  C^o  H30  Oo  S.  The  carvols  from  the  two  oils  also  cor- 
x-espond  in  their  optical  properties.  They  do  not  differ  more  in  smell 
than  many  sorts  of  turpentine  oil,  or  oil  of  citron  and  oil  of  lemon. 

The  author  examined  a  sample  of  oil  of  Meutha  crispn,  and  found 
it  to  rotate  9-3°  to  the  left.  Treated  with  sulphuretted  hydrogen,  it 
gave  the  crystals  Coq  H3Q  O^  S.  The  liquid  portion,  after  separation 
of  the  alcohol  and  sulphuretted  hydrogen  by  a  gentle  heat,  amounted 
to  about  70  per  cent,  of  the  crude  oil,  and  showed  a  diminished 
rotatory  power  (7-0°  to  the  left).  The  portion  not  acted  upon  by 
sulphuretted  hydrogen  gradually  deposited  crystals  in  the  cold  ;  and 
upon  continuing  the  passage  of  sulphuretted  hydrogen,  adding  a 
little  ammonia,  a  thick  oil  separated,  which,  after  washing,  formed 
a  vitreous  mass  (Coq  H3Q  S3,  or  (C^q  H^^  S)o  S  Ho),  the  hydrothion  sul- 
pho-carvol  or  thiocarvum  first  obtained  by  Varrentrapp  from  cumin 
oil  carvol.  This  compound,  so  very  rich  in  sulphur,  has  at  first  an 
agreeable  spicy  smell,  but  when  purified  is  odourless.  As  the  oil  of 
Meutha  crlspa  rotated  the  plane  of  polarization  to  the  left,  it  would 
result  that  the  carvol  it  contained  would  also  have  algevogyre  action, 
although  chemically  it  was  perfectly  identical  with  carvol  from  cumin 
oil.  The  author  had  supposed  that  the  rotatory  powers  of  the  two 
carvols  might  be  equal,  but  exercised  in  opposite  directions.  Ex- 
amined, however,  under  the  same  conditions  as  those  before  men- 
tioned for  cumin  carvol,  the  crisped  mint  carvol  showed  a  deviation 
to  the  left  of  about  9°  only.  It  would  be  interesting  to  compai'e 
these  two  carvols  still  more  closely,  as  the  author  thinks  that  that 
from  crisped  mint  would  probably  also  yield  an  oxycymene  (carva- 
crol)  without  optical  action,  as  well  as  other  derivatives  identical 
with  those  from  cumin  carvol. 

The  author  has  not  met  with  carvol  in  any  other  case,  although 
he  has  examined  a  large  number  of  essential  oils. 

Hesperidin.  E.  Paterno  and  Gr.  Briosi.  {Ber.  cler  deutsch. 
Chem.-Ges.,  ix.,  250-252.)  From  four  thousand  ripe  oranges  the 
authors  obtained  180  grams  of  pure  hesperidin.  Their  process  for 
the  pi'eparation  of  this  substance  deviates  but  little  from  the  one 
described  in  the  Year-Booh  of  Pharmacy,  1876,  153.  It  can  also  be 
obtained  from  the  ripe  fruit  of  Citrus  llinunum  and  Citrus  media. 


5-t  YEAR-BOOK    OF    PHARMACY. 

Pare  hesperidin  fuses  at  243°-245°.  It  is  nearly  insoluble  in  water, 
dilute  acids,  and  ether  ;  but  freely  soluble  in  alkalies  and  in  aniline. 
From  its  alkaline  solutions  it  is  precipitated  by  acids,  and  from  solu- 
tions in  aniline  by  ether. 

HesperidilL  E.  Hoffmann.  (Ber.  der  deutsch.  Chem.-Ges.,  ix., 
685.)  The  composition  of  this  glucoside  is  represented  by  the 
formula  C^,  H^g  O^^.  When  treated  with  dilute  acids  it  yields  glucose 
and  a  substance  named  hesperetin,  Cig  Hjj  Og,  which  is  split  up  by 
caustic  potash  into  phloroglucin,  CgHgOg,  and  hesperitic  acid, 
Cjo  HjQ  O4.  The  latter  fuses  at  225°,  but  begins  to  sublime  before 
the  fusing  point  is  reached  ;  when  fused  with  caustic  potash  it 
yields  protocatechuic  and  acetic  acids.  During  its  sublimation  it 
is  partially  decomjjosed,  with  the  formation  of  a  body  resembling 
vanilhn.  Neutral  solutions  of  its  salts,  but  not  solutions  of  the  free 
acid,  produce  a  cinnamon  brown  precipitate  with  ferric  chloride. 

Hesperetin  fuses  at  223°.  It  forms  white  crystals,  having  a 
sweet  taste  and  being  insoluble  in  cold  water,  but  soluble  in  alcohol 
and  ether. 

The  Manufacture  of  Nitric  Acid.  H.  Gobel.  (Dingl.  pohjt. 
Journ.,  ccxx.,  238-245;  Journ.  Chem.  tSoc,  Sept.,  1876,  332.) 
Proposals  have  been  made  and  methods  devised  for  the  decomposi- 
tion of  the  sodium  nitrate  (Chili  saltpetre)  ;  so  that  instead  of  sul- 
phuric acid,  some  other  decomposing  substance  should  be  used,  such 
as — besides  leaving  behind  a  valuable  residue — shall  afford  a  good 
yield  of  acid.     The  best  of  these  are  the  following : — 

(R.  Wagner.) — Heating  a  mixture  of  alumina  hydrate  with 
sodium  nitrate. 

(J.  Walz.) — Heating  sodium  nitrate  with  calcium  carbonate  and 
steam  in  retorts. 

(Kiihlman.) — Heating  sodium  nitrate  with  manganese  chloride,  etc. 

All  these  proposed  methods  have  simply  remained  proposals,  none 
being  found  of  sufficient  merit  as  yet  to  replace  the  method  by 
which  nitre  is  decomposed  with  sulphuric  acid. 

However,  the  plant  and  apparatus  used  in  the  above  universal 
method,  have  undergone  from  time  to  time  considerable  improve- 
ments. Thus  the  old  deep,  elliptical  pans,  with  stoneware  lids,  etc.. 
have  been  replaced  by  cast-iron  cylinders,  which  are  set  up  on  their 
sides.  These  have  been  found  to  pos.sess  many  advantages,  as  they 
require  comparatively  little  fuel,  are  easily  managed,  and  do  not  per- 
mit loss  of  gas  at  the  joints,  these  being  reduced  to  minimum  (they 
are  lined  inside  with  fire-clay  tiles,  cemented  with  acid-proof  cement) . 

Another  improvement,  now  an  old  one,  is  the  fractional  distilla- 


PHARMACEUTICAL    CHEMISTRY.  55 

tion  of  the  acid,  by  which  means  the  production  of  a  colourless  con- 
centrated acid  was  made  possible. 

Then  the  old-fashioned  earthenware  head-piece  and  pipes  were 
replaced  by  glass  tubes ;  so  that  the  reaction,  and  procedui*e  of  the 
distillation  could  be  observed,  and  the  danger  of  frothing  or  boiling 
over  reduced  or  removed. 

In  earlier  times,  the  receivers,  consisting  of  earthenware  or  stone- 
ware vessels,  were  frequently  cracked  or  broken,  with  loss  of  vapours 
or  acid,  or  both.  It  was  necessary  to  moderate  the  action  very 
considerably  to  prevent  overheating  of  these  condensers ;  and  this 
meant  loss  of  time,  labour,  and  a  reduced  yield.  To  avoid  these 
evils,  R.  Wagner  proposed  the  employment  of  a  series  of  funnel- 
shaped  earthenware  bottles,  through  which  system  the  acid  vapours 
circulate,  accompanied  by  a  stream  of  water.  The  author  considers 
it  questionable  if  the  cooling  of  the  distillate  was  sufficiently  at- 
tained by  these  means.  Another  plan  to  avoid  the  cracking  of  the 
receivers,  was  to  allow  the  heated  gases  from  the  firing-up  apparatus 
attached  to  the  decomposing  vessel  to  pass  under  the  condensers, 
and  so  to  warm  them  before  escaping  to  the  chimney. 

In  England  a  still  greater  improvement  was  made,  viz.,  the  ad- 
dition of  a  stoneware  worm  and  condenser,  through  which  the  gases 
passed  from  the  decomposer  before  entering  the  receivers.  This 
precaution  prevented  the  breaking  of  the  receivers,  or  at  least 
greatly  reduced  it.  The  apparatus  used  by  the  author  with  great 
success  for  cooling  the  gases,  consists  simply  of  a  straight  glass  tube, 
bent  at  both  ends,  which  lies  in  constantly  renewed  water.  One  end 
of  the  tube  is  connected  with  the  tube  of  the  decomposition  appara- 
tus ;  the  other  with  the  first  receiver.  This  simple  arrangement  has 
enabled  the  author  to  decompose  (with  fractional  distillation)  250 
kilos,  of  saltpetre  in  36  houi's ;  and  with  no  fractional  distillation, 
300  kilos,  in  36  hours. 

Besides  this,  the  receivers  could  be  diminished  in  number  from  9 
to  3,  most  of  the  acid  collecting  in  the  first  receiver.  Also,  it  is 
thus  easy  to  obtain  very  concentrated  acid.  Experiments  showed 
that  in  a  cylinder  apparatus  there  were  obtained  in  th.e  first  receiver 
140  kilos,  of  acid  of  sp.  gr.  1-53,  temperature  about  60°.  In  the 
second,  55  kilos,  of  acid  of  sp.  gr.  1-49.  In  the  last  receiver,  the 
acid  had  a  sp.  gr.  of  1'32. 

In  six  months  only  one  cooling  tube  was  broken.  It  is  shown  by 
numerical  data  given,  that  by  this  careful  method  of  cooling,  an  in- 
creased production  is  obtained  of  6"8  kilos,  of  acid  of  sp.  gr.  1'33, 
per  100  kilos,  of  sodium  nitrate. 


66 


TEAR-BOOK    OF    PHARMACY. 


At  the  end  of  the  apparatus,  i.e.,  in  connection  with  the  last  re- 
ceiver, is  placed  a  tower  of  earthenwai-e  tubes  filled  with  coke  soaked 
in  concentrated  sulphuric  acid,  by  which  means  the  nitrous  gases, 
otherwise  lost,  are  absorbed.  In  fact,  the  arrangement  is  simply  a 
small  Gay-Lussac's  tower. 

A  useful  table  is  given,  showing  the  increase  of  density  of  nitric 
acid  on  cooling  from  any  likely  temperature  to  155°C. 


I. 

II. 

I. 

II. 

I. 

II. 

Increase  on 

Increase  on 

Increase  on 

Temperature. 

cooling  to  15° 

Temperature. 

cooling  to  1.5° 

Temperature. 

cooling  to  15° 

in  deg.  Banm^. 

in  deg.  Baumd. 

in  deg.  Baumd. 

45-0 

3-65 

35-0 

210 

25-0 

0-90 

44-5 

3-56 

34-5 

1-98 

24-5 

080 

44-0 

3-48 

34-0 

1-92 

240 

0-76 

43-5 

3-40 

335 

1-85 

23-5 

0-72 

43-0 

3-32 

330 

1-79 

230 

0-67 

42-5 

3-23 

32-5 

1-73 

22-5 

0G3 

42-0 

315 

32-0 

1-67 

22-0 

0-59 

41-5 

3-08 

31-5 

1-62 

21-5 

0-55 

410 

3  00 

31-0 

1-56 

210 

0-52 

40-5 

2-92 

30-5 

1-50 

20-5 

0-48 

40-0 

2-85 

30  0 

1-45 

200 

0-45 

39-5 

2-73 

29-5 

1-34 

19-5 

036 

890 

2-65 

29-0 

1-29 

190 

0-33 

38-5 

2-58 

28-5 

1-23 

18-5 

0-29 

38  0 

2-50 

28-0 

118 

18-0 

0-25 

37-5 

2-43 

27-5 

1-13 

17-5 

0-20 

37  0 

2-36 

270 

1-08 

170 

013 

36-5 

2-29 

26-5 

103 

16-5 

0-07 

36-0 

2-23 

260 

0-99 

16-0 

005 

35-5 

2-16 

25-5 

0-94 

15-5 

0-02 

Suppose,  for  example,  an  acid  is  examined  and  found  to  be  of  a 
specific  gravity  of  36°  Baume,  and  its  temperature  is  40° ;  if  this  be 
cooled  to  15°,  it  will  naturally  become  denser,  and  to  the  extent  of 
2-85°  B.,  its  density  at  15°  being  36  +  2-85  =  38-85°  Baume. 

Determination  of  Nitric  Acid  by  Indigo.  R.  Warington. 
(Chem.  News,  xxxv.,  45-47,  57-59.)  The  author  first  describes  the 
method  employed  by  Boussingault,  in  which  the  nitrate  is  boiled 
with  hydrochloric  acid,  and  solution  of  indigo  added  till  a  sap-green 
colour  is  permanently  obtained.  Boussingault  destroj's  organic 
matter,  when  present,  by  a  preliminary  distillation  with  peroxide  of 
manganese  and  sulphuric  acid.  The  experiments  made  by  the 
author  with  the  method  introduced  by  Marx,  and  since  improved 
by  Trommsdorff,  Goppelsroeder,  Bemmelen,  and  Sutton,  are  next 
detailed.  In  this  method  the  reaction  is  brought  about  by  mixture 
with  oil  of  vitriol,  without  the  use  of  artificial  heat.     The  indigo 


PHARMACEUTICAL    CHEMISTRY.  0/ 

employed  was  a  solution  of  "  indigo-carmine  "   (sulphiudigotate  of 
sodium)  ;    the   solution   of  pure    nitre  contained  O'OlOll    gram  in 
10  c.c;  the  oil  of  vitriol  was  distilled  acid. 
The  author  found  : — 

1.  That  the  maximum  amount  of  indigo  is  consumed  only  when 
a  sufficiency  of  indigo  is  present  with  the  niti'ate  before  the  addition 
of  oil  of  vitriol.  The  plan  adopted  by  Marx  of  mixing  the  nitrate 
solution  with  twice  its  volume  of  oil  of  vitriol,  and  then  im- 
mediately running  in  the  indigo,  always  consumes  less  indigo  than 
the  nitrate  is  capable  of  oxidising.  The  full  amount  of  indigo  can 
only  be  ascertained  by  a  series  of  approximating  experiments,  in 
which  the  oil  of  vitriol  is  suddenly  added  to  the  previously  mixed 
nitrate  and  indigo. 

2.  The  amount  of  indigo  required  depends  greatly  on  the  propor- 
tion of  sulphuric  acid  present,  and  within  certain  wide  limits  the 
amount  of  indigo  is  less  as  the  proportion  of  sulphuric  acid  is 
greater.  With  10  c.c.  of  nitre  solution,  11'3  c.c.  of  indigo  were 
required  when  the  indigo  and  nitre  were  mixed  with  their  own 
volume  of  oil  of  vitriol;  but  8'9  c.c.  of  indigo  were  sufficient  when 
two  volumes  of  oil  of  vitriol  wei-e  employed. 

3.  The  full  amount  of  indigo  is  consumed  only  when  the  tempera- 
ture of  the  mixture  remains  sufficiently  high  during  the  reaction : 
100°,  110°,  and  120°,  are  given  by  various  writers  as  the  minimum 
temperature.  When  the  reaction  was  immediate,  artificial  heat  was 
found  necessary  ;  but  when — through  dilution  of  the  nitrate,  small 
volume  of  the  liquid,  weakness  of  the  vitriol,  etc. — the  reaction  was 
tardy,  the  temperature  of  the  flask  containing  the  mixture  must  be 
maintained  by  a  paraffin  or  chluride  of  calcium  bath,  or  the  results 
will  be  too  low. 

4.  The  true  tint  of  final  reaction  is  a  dull  brown,  which  precede 
the  commencement  of  green ;  the  brown  tint  becomes  green  when 
suddenly  diluted  with  water.     If   a  solution  of  sublimed  indigotine 
in  sulphuric  acid  is  employed,  the  tint  passes  at  once  from  gold  to 
green  without  an  intermediate  brown  stage. 

5.  When  a  nitrate  solution  is  diluted,  it  apparently  requires  dis- 
tinctly less  indigo  per  unit  of  nitrate  if  a  double  volume  of  oil  of 
vitriol  be  employed ;  but  if  a  single  volume  is  used,  the  ditference  is 
very  slight,  and  in  the  contrary  direction.  If  two  volumes  of  sul- 
phuric acid  are  employed,  the  indigo  must  therefore  be  standardized 
with  nitre  solutions  of  several  dilutions,  to  ascertain  the  value  of 
different  parts  of  the  scale. 

6.  The  influence  of  chlorides   is   slightly  to  diminish  the   indigo 


58 


YEAR-BOOK    OF    riTARMACY. 


required.  AVith  '03  to  lO  gram  of  chloride  of  sodium  in  10  c.c.  of 
nitre  solution,  the  reducing  effect  of  100  chloride  of  sodium  was 
equiil  to  1"1G  nitre.  With  much  chloride  the  final  tint  is  a  bright 
green. 

7.  Some  kinds  of  organic  matter  have  a  powerful  reducing  action. 
Cane-sugar  had  a  greater  etiect  the  larger  the  proportion  of  sulphuric 
acid  and  the  more  dilute  the  nitrate;  with  a  one-tenth  nitre  solution, 
and  a  double  volume  of  oil  of  vitriol,  100  of  sugar  had  a  reducing 
effect  equal  to  G2  3  nitre.  The  soluble  humic  matter  of  soils  was 
apparently  without  influence, — determinations  of  nitrate  in  a  kitchen 
garden  soil  by  the  mercury  method,  and  by  the  indigo  method, 
giving  accordant  results.  Only  one  volume  of  sulphuric  acid  was 
used  in  this  experiment. 

Volumetric  Estimation  of  Bismuth.  M.  M.  Pat ti son  Muir. 
(Abstract  of  a  paper  read  before  the  Chemical  Society:  Journ.  Ghent. 
Soc,  1876,  483.)  The  process  described  by  the  author  depends  upon 
the  facts  concerning  the  formation  of  chromate  of  bismuth  made 
known  by  Lowe  (Journ.  PraJd.-Chem., Ixvii.,  288  and  463).  Potassium 
chromate  or  potassium  dichromate  solution  is  ran  into  a  nearly 
neutral  solution  of  bismuth  nitrate  until  the  whole  of  the  metal  is 
precipitated  in  the  form  of  chromate.  The  final  point  of  the  re- 
action is  determined  by  bringing  a  drop  of  the  supernatant  yellow 
liquid  into  contact  with  a  drop  of  the  silver  nitrate  solution  upon  a 
white  slab,  when  red  silver  chromate  is  produced. 

On  account  of  the  uncertainty  which  still  exists  in  reference  to 
the  exact  composition  of  the  chromates  of  bismuth,  and  also  on 
account  of  the  fact  that  a  slight  excess  of  either  of  the  potassium 
chromates  appears  necessary  in  order  to  cause  the  complete  precipi- 
tation of  the  bismuth  salts,  no  attempt  was  made  to  calculate  the 
exact  quantity  of  chromate  needed  to  precipitate  a  known  weight  of 
bismuth,  and  upon  such  a  c.ilculation  to  base  the  composition  of 
a  standard  liquid ;  but  the  plan  was  adopted  of  titrating  a  dilute 
chromate  solution  against  a  standard  bismuth  solution,  and  from 
these  results  calculating  the  strength  of  the  chromate  in  terms  of 
bismuth  precipitated. 

The  author  first  describes  the  results  of  the  experiments  made 
with  a  solution  of  potassium  chromate.  The  chromate  was  purified 
by  recrystallization  from  aqueous  solution.  About  10  grams  were 
dissolved  in  1000  c.c  of  water.  A  solution  of  bismuth  nitrate  was 
prepared  by  dissolving  a  known  weight  of  pure  bismntliic  trioxide 
(Bi|,  O3)  in  dilute  nitric  acid,  and  making  up  the  liquid  to  1  litre. 
The   chromate   solution  was  run  into  a  measured  quantity  of  the 


» 


PHARMACEUTICAL    CHEMISTRY.  59 

bismuth  containing  liquid  (made  nearly  neutral  with  ammonia  and 
maintained  at  the  boiling  point)  until  a  faint  reddish  colour  was 
produced  on  bringing  a  drop  of  the  supernatant  liquid  in  contact 
with  a  drop  of  an  aqueous  solution  of  silver  nitrate  spotted  upon  a 
glass  plate  which  rested  upon  a  sheet  of  white  paper. 

Partial  neutrahzation  of  tlie  acid  liquid  containing  bismuth  was 
effected  by  dropping  in  ammonia  until  a  very  faint  precipitate  was 
formed,  then  boiling  the  liquid,  and  continuing  to  add  ammonia  very 
carefully  until  the  solution  was  but  slightly  acid.  Before  this  point  was 
reached,  a  precipitate  invariably  formed ;  but  it  was  found  that  this 
did  not  interfere  with  the  results.  If  an  excess  of  ammonia  were 
inadvertently  added  it  was  found  better  to  add  nitric  acid  in  quantity 
sufficient  to  dissolve  the  precipitate,  and  again  to  nearly  neutralize 
with  ammonia,  rather  than  to  add  merely  such  a  quantity  of  nitric 
acid  as  should  cause  but  a  faint  acid  reaction  in  the  liquid.  The 
chromate  was  run  in  from  a  burette  graduated  in  tenths  of  a  cubic 
centimetre  and  furnished  with  a  glass  stop-cock.  After  the  addition 
of  a  few  drops  of  chromate  solution,  the  liquid  was  boiled  for  some 
minutes  and  the  precipitate  was  then  allowed  to  settle ;  which  it 
did  very  rapidly  and  completely.  In  order  to  bring  a  drop  of  silver 
nitrate  solution  on  to  the  glass  plate  and  at  the  same  time  to  pre- 
vent the  continued  exposure  of  this  solution  to  the  air  of  the 
laboratory, — an  exposure  which  always  resulted  sooner  or  later  in 
the  production  of  silver  sulphide  in  the  solution, — a  special  apparatus 
was  made  use  of,  by  which  the  formation  of  silver  sulphide  was 
reduced  to  a  minimum.  The  formation  of  silver  chromate  only 
became  apparent  after  a  few  moments,  and  when  an  excess  of  silver 
nitrate  was  used  relatively  to  the  quantity  of  potassium  chromate  in 
the  drop  of  liquid. 

Two  series  of  experiments  were  performed:  one  with  potassium 
chromate,  the  other  with  the  dichromate.  The  dichromate  method 
proved  to  be  the  better  one  of  the  two,  and  yielded  very  satisfactory 
results.  The  dichromate,  moreover,  is  more  easily  purified  by  re- 
crystallization  than  the  chromate.  The  reaction  with  silver  nitrate 
is  more  marked  than  in  the  case  of  the  chromate,  but  a  slight  excess 
of  silver  nitrate  should  here  also  be  added,  and  a  little  time  should 
be  allowed  to  elapse  before  a  conclusion  is  di'awu  as  to  the  comple- 
tion of  the  process.  The  difference  between  the  quantities  of 
bismuth  taken  and  the  quantities  found  are  smaller  in  the  results 
obtained  by  the  dichromate  than  in  those  obtained  by  the  chromate 
method.  It  is  necessary  to  neutralize  the  greater  part  of  the  free 
nitric  acid  before  running  in  the  dichromate  liquid. 


60  YEAR-BOOK    OP    PlIARJIACY. 

Xo  definite  results  could  be  obtained  in  the  presence  of  chlorides, 
as  the  precipitate  then  t'oriued  was  totally  unlike  the  chrouiate  of 
bismuth  usually  obtained ;  it  was  white  or  light  yellow,  heavy,  and 
granular,  and  consisted  probably  to  a  large  extent  of  oxychloride. 
As  this  process  is  not  applicable  in  the  presence  of  other  metals, 
such  as  copper,  arsenic,  and  calcium,  such  metals — if  existing  in 
solution  along  with  bismuth — must  first  be  removed  by  the  ordinary 
method.  This  being  done,  the  bismuth  may  then  be  titrated  with 
perfect  accuracy. 

Preparation  of  Lithium  Carbonate  from  Lepidolite.  F.  Fil- 
singer.  (^Arcliiv  der  PJiarin.,  v.,  198.)  The  lepidolite,  reduced  to 
fine  powder,  is  treated  with  strong  sulphuric  acid,  containing 
some  nitric  acid,  in  a  large  brick  trough,  at  a  gentle  heat.  It  is 
heated  "with  constant  stirring  till  it  gains  consistency  enough  to  be 
made  into  balls,  which  can  be  easily  introduced  into  a  reverbe- 
ratory  furnace.  The  slight  excess  of  sulphuric  acid  is  driven  off 
at  a  gentle  heat;  the  temperature  then  raised,  and  the  pieces 
vv-hilst  still  hot  are  treated  with  water  in  vessels  lined  with  lead. 
The  residue  consists  of  almost  pure  silica,  for  which  a  market  is 
easily  found.  As  lithium  does  not  replace  potassium  in  alum,  a 
sufficient  quantity  of  potash  is  added  to  transform  all  the  sulphate 
of  aluminium  present  into  alum.  On  evaporation  the  alum  separates 
in  powder.  It  "is  removed,  dried  in  a  centrifugal  machine,  and  on 
recrystallization  is  obtained  in  fine  crystals.  The  excess  of  alumina 
is  precipitated  from  the  mother-liquor  by  milk  of  lime,  and  the 
excess  of  sulphuric  acid  by  barium  chloride.  The  barium  sulphate 
obtained  is  a  marketable  article.  The  liquid  is  then  evaporated, 
and  the  mixed  chlorides  of  lithium,  potassium,  sodium,  calcium 
and  sometimes  barium,  exhausted  with  absolute  alcohol.  The 
lithium  and  calcium  chlorides  are  dissolved.  The  calcium  is  sepa- 
rated as  oxalate,  and  the  lithium  chloride  evaporated  and  crystal- 
lized. It  is  precipitated  with  ammonium  carbonate  and  ammonia, 
and  brought  into  the  market  in  the  form  of  carbonate.  The  advan- 
tages of  this  pi'ocess  are,  complete  consumption  of  the  crude  material, 
cheap  reagents,  common  plant,  precipitates  which  are  easily  washed, 
and  a  number  of  marketable  chemicals,  e.g.,  silica,  alumina,  potash, 
alum,  and  lithium  carbonate. 

Constituents  of  Black  Pepper.  Prof.  R.  Buchheim.  (Mew 
liemedies,  !Sei)tember,  18 7G.)  Several  years  ago  the  author  has 
shown  that  black  pepper  contains  two  substances  which  are  of 
analogous  chemical  constitution,  and  have  a  similar  action.  (ArcMv 
fur  Pathul.-AHutoinie,  Ivi.,  9.)      One  of  these  is  piperin,  which  was 


PHARMAUEDTICAL    CHEMISTRY.  61 

discovered  by  Oersfcedt  in  1819,  and  was  first  supposed  to  be  the  acrid 
principle,  until  Pelletier  (1821)  showed  that  it  was  tasteless  when 
quite  pui'e,  and  that  the  biting  taste  resided  in  the  accompanying  resin. 
To  settle  this  question,  Professor  Buchheim  lately  exhausted  2000 
grams  of  black  pepper  with  alcohol,  removed  the  alcohol  from  the 
percolate  by  distillation,  and  treated  the  residue  with  water,  which 
dissolved  only  traces  thereof,  without  assuming  any  sharp  taste. 
The  extract  was  now  shaken  with  ether  as  long  as  the  latter  became 
coloured  thereby.  The  residuary  part  of  the  extract  consisted 
almost  wholly  of  impure  piperin,  which  was  deprived  of  a  little 
adhering  resin  by  potassa  solution,  then  dissolved  in  hot  alcohol, 
decolorized  by  animal  charcoal,  and  recrystallized  from  hot  alcohol 
and  petroleum  ether.  The  pure  piperin  thus  obtained  consists  of 
almost  colourless  rhombic  cylinders,  with  a  faint  yellowish  tint, 
which  could  not  be  removed.  They  were  tasteless  when  merely 
placed  upon  the  tongue,  being  entirely  insoluble  in  aqueous  fluids  ; 
but  exhibited  the  sharp  taste  of  pepper  when  chewed,  or  when 
introduced  in  alcoholic  solution. 

The  ethereal  solution  obtained  above  was  then  shaken  with  solu- 
tion of  potassa,  which  removed  chlorophyll,  fatty  acids,  and  an  acid 
resin.  On  distilling  off  the  ether  a  residue  of  an  intense  yellow 
colour  was  left  behind,  which  was  dissolved  in  alcohol  and  treated 
with  animal  charcoal.  It  was,  however,  impossible  to  decolorize  it 
entirely  ;  and,  besides,  a  little  piperin  accompanied  it,  from  which 
it  was  exceedingly  diflicult  to  separate  it.  In  this  condition  the 
residue  appeared  as  a  yellowish  brown  mass  of  the  consistence  of 
thick  turpentine,  and  of  extremely  biting  taste.  The  yield  was 
about  two-thirds  that  of  piperin.  Treatment  with  alcoholic  potassa 
and  supersaturation  with  sulphuric  acid,  produced  from  it  a  sub- 
stance which  was  recognised  as  piperidin  sulphate. 

There  exist,  therefore,  in  black  pepper,  two  bodies,  which  yield 
piperidin  with  alcoholic  potassa  ;  namely,  piperin,  and  the  new 
body  here  obtained,  for  which  the  name  chavicin  is  proposed,  from 
Chavica  nfficinarum,  Mign.,  or  long  pepper.  On  account  of  its 
amorphous  condition,  this  substance  has  heretofore  been  denoted 
merely  as  "  resin,"  and  had  not  been  investigated.  While  piperin  may 
be  regarded  as  piperidin,  C5  H^q  H  N,  in  which  one  H  is  replaced  by 
piperic  acid — C5  H^q  (^inHg  0.,)  N" — we  may  consider  chavicin  in  a 
similar  manner  as  piperidin,  in  which  one  H  is  replaced  by  chavicic 
acid. 

These  piperidin  compounds  exist  in  nature,  also,  in  other  plants. 
Pellitory  {^radix  pyrethi'i)  contains  a  body  which   Professor  Buch- 


62  YEAR-BOOK    OF    PHARMACY. 

heim  has  named  pyrethrin,  and  whicli  he  ascertained  to  bo  decom- 
posable into  piperidin  and  pyrethric  acid.  Herha  spilanthis  (from 
Spilanthes  oleracea,  Jacq.,  paracress)  also  contains  a  body  which 
may  be  split  np  into  an  acid  and  piperidin. 

Peptone.  (Fi'ora  New  Bemedirs,  August,  187G.)  The  terra  "  Pep- 
tone "  is  used  to  denote  those  albumen  or  protein-bodies  which  have 
been  altered  by  the  gasti'ic  juice,  or  in  other  words,  the  result  of  the 
action  of  pepsin  upon  fibrin  or  albumen.  Peptones  introduced  into 
the  digestive  organs  are  directly  absorbed  iuto  tlie  blood,  without 
having  to  undergo  previous  digestion,  and  are  converted  into 
albumen-bodies.  As  there  are  various  diseases  in  which  the  secre- 
tion of  normal  gastric  juice  is  more  or  less  diminished,  or  entirely 
suppressed, — preventing,  therefore,  the  assimilation  of  the  protein 
compounds, — the  nutrition  of  the  system  may  still  be  accomplished 
by  introducing  peptones  into  the  digestive  canal.  The  importance 
of  this  mode  of  administering  nourishment  in  typhous  and  gastric 
diseases  is  fully  recognised  by  physicians. 

The  German  peptone  is  sold  in  round  tin  cans  weighing  340  grams 
(12  oz.  avoird.),  and  containing  250  grams  (9  oz.  avoird.)  of  material. 
Dr.  Hermann  Hager  suggests  the  following  method  of  examining  it : 
10  volumes  of  the  peptone  are  slightly  warmed,  mixed  in  a  large  test 
tube  with  GO  volumes  of  a  concentrated  solution  of  sodium  chloride, 
and  the  mixture  set  aside.  After  the  lapse  of  thirty  minutes  the  pep- 
tone has  collected  at  the  bottom  of  the  liquid,  and  occupies  8  to  9 
volumes  ;  after  thirty  minutes  more  7  to  8  volumes;  and  after  twelve 
hours  not  less  than  3 "3  volumes.  Peptone  in  a  thin  layer  is  a  clear 
liquid  of  the  consistence  of  thin  syrup,  and  has  a  faintly  bitter  taste, 
somewhat  resembling  that  of  extract  of  beef  or  of  mushrooms.  A 
peptone-chocolate  is  also  manufactured;  this  is  of  dark  brown  colour, 
has  the  consistence  of  a  soft  extract,  and  is  sold  in  the  same  kind  of 
tin  boxes  as  the  peptone  itself, 

Hager  quotes  the  following  extract  from  a  report  of  Dr.  H.  San- 
ders, in  Amsterdam  (who  is  also  a  manufacturer  of  peptone)  :  "  It 
is  well  known  that  the  albuminoid  substances  are  the  most  import- 
ant nourishing  agents  of  the  animal  body.  From  them  the  muscles 
and  nerves  draw  the  necessary  material  for  their  constant  rccon- 
stmction  during  the  process  of  life.  But  before  these  albuminoids 
can  become  of  any  use  to  the  body,  they  must  be  digested ;  and  this 
is  done  by  being  converted  into  peptone  in  the  stomach  and  intes- 
tinal canal.  As  peptone  it  is  taken  up  by  the  blood,  and  there 
reconverted  into  albumen.  As  soon  as  any  peptone  has  been  formed 
it  is  very  rapidly  absorbed.     Whenever  digestion  is  defective,  or  the 


PHARMACEUTICAL    CHEMISTRY.  G3 

gastric  juice  is  of  abnormal  character,  it  is  readily  understood  tbat 
the  conversion  of  albumen  or  fibrin  into  peptone,  and  hence  nutrition 
in  general,  must  become  impaired. 

"  This  defect  may  be  removed  by  introducing  ready-made  peptone, 
which  is  rapidly  and  completely  absorbed  by  the  body,  and  which 
requires  no  further  digestion.  For  this  reason  it  is  just  as  effective 
if  administered  by  the  rectum  as  if  introduced  into  the  stomach;  and 
in  many  cases  the  former  way  is  alone  practicable. 

"The  only  disngreeable  point  about  peptone  is  its  taste,  and  if 
given  by  the  mouth  this  may  require  correction.  In  the  case  of 
nursing  infants,  it  is  sufficient  to  add  it  to  the  milk,  about  one  or  two 
tablespoonfuls  to  the  quart.  By  beginning  with  small  quantities, 
say  one  teaspoonful,  they  become  easily  accustomed  to  it.  Adults 
may  take  it  in  milk,  or  diluted  with  water,  or  beef  tea ;  or  it  may  be 
mixed  with  equal  parts  of  sherry,  madeira,  or  some  other  generous 
wine.  Tlie  most  agreeable  mode  of  administration,  however,  is  the 
following  : — 

^'Peptone  Chocolate. — 250  grams  (9  oz.avoird.)  of  peptone  are  gently 
heated,  and  200  grams  (7  oz.)  of  white  sugar  dissolved  in  it ;  to  the 
warm,  solution  are  added,  under  constant  stirring,  100  to  125  grams 
(S^  to  4 J  oz.)  of  pure  pulverized  chocolate  (free  from  oil),  until 
there  is  produced  a  homogeneous  syrupy  mass,  which  may  be  fla- 
voured with  vanilla,  essence  of  orangfe  or  of  lemons.  On  coolino-  this 
mixture  may  be  kept  for  a  long  time  without  spoiling,  and  a  portion 
may  be  dissolved  in  hot  water  or  milk.  When  administering  it  per 
rectum  it  should  be  diluted  with  four  to  six  parts  of  warm  water." 

Expulsion  of  Sulphuretted  Hydrogen  from  its  Solutions  by  Boiling. 
J.  Volhard.  {Zeitschr.  fur  Anahjt.-Ghem.,  1876,  341.)  It  appears 
from  the  author's  experiments  that  sulphuretted  hydrogen  cannot 
be  completely  expelled  from  its  aqueous  solution,  even  by  long  con- 
tinued boiling.  After  boiling  the  solution  in  a  flask  for  five  hours, 
during  which  the  water  lost  by  evaporation  was  gradually  replaced, 
the  resulting  liquid  still  contained  0"003  per  mille  of  H.,  S.  Solu- 
tions which  were  boiled  down  to  one-tenth  of  their  original  volumes 
yielded  residues  containing  0'0015-0'0016  per  mille  of  the  gas. 

The  Colouring  Matter  in  the  Petals  of  Eosa  Gallica.  H.  Senier. 
(From  a  paper  read  at  the  Pharmaceutical  Society's  meeting,  Feb- 
ruary 1st,  1877.) 

Extraction. — The  dried  petals  of  commerce  were  first  digested  with 
ether,  and  the  ethereal  solution  removed  by  filtration.  By  this 
treatment  quercitrin — the  yellow  colouring  matter — and  solid  fat  were 
removed  (Pilhol).     Experiments  were  next  made  to  ascertain  the 


64  YEAR-BOOK    OP    PHARMACY. 

relative  value,  as  solvents  of  the  colouring'  matter,  of  chloroform, 
water,  and  alcohol.  No  colouring  matter  was  dissolved  by  the  chlo- 
roform. Hot  water  dissolved  it  freely,  but  dissolved  also  much 
albuminous  matter.  Alcohol  was  found  decidedly  the  best,  yielding 
a  solution  comp;iratively  free  from  other  substances.  But  while  the 
solution  in  water  is  of  a  bright  red  colour,  that  in  alcohol  is  at  first 
colourless — due  most  likely  to  some  reducing  action  of  the  alcohol — 
but  acquires  in  time  a  red  tint,  which  brightens  with  age.  From  this 
alcoholic  solution  the  colouring  matter  was  precipitated  in  a  green 
amorphous  state  by  acetate  of  lead.  This  precipitate,  after  washing 
and  drying  (100°  C),  was  treated  in  two  ways  : — Firstly,  the  precipi- 
tate, suspended  in  rectified  spirit,  was  decomposed  by  sulphuretted 
hydrogen,  and  the  mixture  filtered  (Eisner).  Secondly,  the  precipi- 
tate, suspended  in  rectified  spirit,  was  decomposed  by  dilute  sulphuric 
acid, — taking  care  to  have  the  precipitate  in  excess, — and  the  mix- 
ture filtered.  Both  these  latter  solutions  have  a  bright  red  colour. 
The  solution  obtained  by  means  of  dilute  sulphuric  acid  was  found 
to  be  the  purer,  though  most  of  the  reactions  detailed  below  may 
be  obtained  from  either,  or  even  from  the  original  alcoholic  solution. 

Action  of  Reagents. — Dilute  acids  deepen  the  colour  ;  but  concen- 
trated they  decompose  it,  concentrated  nitric  yielding  a  yellow  solu- 
tion. Alkalies  change  the  colour  from  bright  red  to  a  deep  red  with 
a  bright  green  fluorescence,  and  when  added  in  excess  give  a  yellow 
solution.  A  drop  of  solution  of  soda  and  a  drop  of  the  solution  of 
colouring  matter,  placed  on  a  glass  slide  and  slowly  evaporated  by  a 
gentle  heat,  yield  under  the  microscope  a  mass  of  well-defined  crys- 
tals. Pota.sh  yields  crystals  when  treated  in  the  same  manner.  Am- 
monia itself  does  not  give  crystals,  but  combined  with  soda  it  does. 
With  potash,  ammonia  gives  with  the  colouring  matter  perfect  octa- 
hedra.  These  crystals  under  the  microscope,  if  treated  with  an 
acid,  yield  the  colouring  matter  in  the  red  form,  which  evidently 
arises  from  the  crystals  not  from  the  solution,  thus  showing  that 
they  are  actual  combinations  of  the  colouring  matter. 

Alkaline  carbonates  act  in  the  same  manner  as  alkalies,  except 
that  the  change  of  colour  is  accompanied  with  effervescence.  Chlo- 
rine entirely  destroys  the  red  colour,  leaving  a  yellow  solution. 
Sulphuretted  hydrogen  changes  the  red  to  brown,  but  does  not  alter 
the  chemical  character  of  the  solution.  Stannic  chloride  changes 
the  red  to  a  beautiful  dark  magenta  colour.  On  boiling  with  metal- 
lic mercury  the  red  colour  is  changed  to  a  dark  violet  or  purple. 

Mercuric  nitrate  and  chloride  both  give  a  slight  white  or  pinkish 
precipitate,  soluble  in  water. 


THARMACEUTICAL    CHEJrrSTRY.  65 

Hydrate  of  bainum  yields  a  yellowish  green  precipitate,  as  does 
also  hydrate  of  calcium,  both  becoming  brown  when  deprived  of 
moistare.  No  precipitates  ai'e  given  by  chloride  of  platinum,  nitrate 
of  silver,  or  the  usual  alkaloidal  reagents,  except  very  slight  ones  by 
iodohydrargyrate  and  trinitrophenic  acid. 

Carbonic  acid  does  not  redden  the  colourless  or  green  modification, 
but  though  possessing  this  property,  esteemed  in  cochineal,  it  does 
not  appear  to  be  practically  useful  as  an  indicator  in  alkalimetry. 

Peroxide  of  hydrogen  appeared  to  give  no  reaction. 

Sulphurous  acid  leaves  the  colour  of  a  brown  shade. 

To  test  paper  all  the  solutions  have  an  acid  reaction. 

Neutral  and  basic  acetates  of  lead  give  precipitates  of  a  colour 
varying  from  a  green  to  a  bluish  green.  These  precipitates,  decom- 
posed by  sulphuric  acid,  yield  the  colouring  matter  to  the  solution, 
as  already  mentioned,  and  deposit  sulphate  of  lead.  The  action  of 
reasrents  leads  to  the  conclusion  that  the  colourinof  matter  is  an 
acid,  and  that  as  such  it  forms  salts — the  crystals  and  precipitates 
described. 

The  analysis  of  the  lead  salt  led  to  the  formula  Pbo  Coj  Hgg  O30. 

The  author's  report  in  the  Pliarmaceutlcal  Journal  (p.  651)  is 
illustrated  by  diagrams  of  crystals  of  the  sodium  salt,  the  ammonio- 
sodium,  and  the  ammonio-potassium  salts.  It  also  contains  diagrams 
of  the  principal  spectra  of  the  colouring  matter. 

Estimation  of  the  Alkaloids  of  Sabadilla  and  Physostigma. 
E.  Masing.  (Archiv  der  Pharm.,  October,  310-317.)  The  authoi* 
has  found  that  pure  veratrine,  dissolved  with  the  requisite  quantity 
of  acid  in  14,670  parts  of  water,  still  yields  with  Mayer's  solution  a 
faint  turbidity  ;  while  on  the  addition  of  1  per  cent.  Hg  S  0^,  the 
limit  of  the  reaction  is  reached  with  a  dilution  of  1  in  11,400. 

The  sabadilline  double  iodide  dissolves  in  17,630  parts  of  pure  water, 
and  in  10,300  parts  of  water  containiug  1  per  cent,  sulphuric  acid. 

Tho  solubility  of  the  hydrargyro-iodide  of  sabatrine  is  greater 
than  that  of  the  preceding  alkaloids  :  in  pure  and  in  acidulated 
water,  containing  1  per  cent.  Ho  S  Op  it  appears  to  be  1  in  2450. 

Commercial  veratrine  gives,  with  Mayer's  solution,  a  more  dis- 
tinct indication  of  alkaloid  than  that  employed  (in  one  case  0*8645, 
instead  of  0'7772  gram  used);  the  cause  for  this  variation,  which 
in  the  presence  of  sabadilline  and  sabatrine  should  be  the  reverse, 
has  not  been  ascertained.  Air- dried  sabadilla  seeds  indicated  an 
amount  of  alkaloids,  which,  if  calculated  as  veratrine,  w^as  equal  to 
3' 61  per  cent. 

Physostigmine,  prepared  by  Vee  and  Leven's  process  (Amer.  Journ. 

F 


66 


YEAR-BOOK    OF    PHARMACY. 


Pharm,  18G5,  204),  ceases  to  react  with  Mayer's  solution  -when 
dissolved  in  9500  parts  of  pure  water,  or  in  8800  parts  of  acidulated 
water,  containing  1  per  cent.  Ho  S  O4.  One  kilogram  of  Calabar 
beans  treated  in  this  manner  yielded  only  0-7482  gram  of  alkaloid  ; 
while  Mayer's  test  solution  indicated,  in  two  experiments,  0'309 
and  (.••433  per  cent,  respectively. 

Action  of  Hydrogen  Sulphide  on  Alkaloids.  E.  Schmidt.  (Lie- 
big's  Amialcn,  clxxx.,  287;  Jonrii.  Chcm.  Soc,  July,  187G.)  Almost 
all  the  known  vegetable  bases  are  acted  upon  by  hydrogen  sulphide. 
The  substances  thereby  formed,  though  in  some  cases  definite  com- 
pounds, appear  for  the  most  part  to  be  mixtures  which  cannot  be 
separated,  owing  to  the  facility  with  which  they  are  decomposed. 
The  author  has  examined  more  particularly  the  compounds  formed 
with  strychnine  and  brucinc. 

Strychnine. — When  an  alcoholic  solution  of  strychnine  is  saturated 
with  hydrogen  sulphide,  and  left  at  rest  for  some  time,  it  gradually 
deposits  fine  orange  red  needles  of  a  substance  to  which  Schmidt 
attributes  the  formula  2  Coj  Ho.  No  Oo,  3  H,  So.  This  substance 
differs  in  colour  and  crystalline  form  from  that  which  Hofmann  ob- 
tained by  the  action  of  ammonium  sulphide  on  strychnine,  but  can- 
not be  distinguished  therefrom  by  analysis.  When  kept  for  a  day 
or  two,  it  gives  off  hydrogen  sulphide,  and  slowly  changes  colour ; 
whereas  Hofmann's  compound  keeps  for  months  without  alteration. 
It  was  ascertained  by  direct  experiment  that  this  compound  is  formed 
only  in  presence  of  oxygen,  not  when  air  is  completely  excluded. 
Its  formation  may  be  represented  by  the  equation  : — 

2  Coi  H.,o  No  Oo  +  6  H,  S  +  30  =  ^''  ^"  !!'  ?:  \  nl  s',  +  3  Ho  O. 

^^^^^^^^^^(hIs.; 

The  compound  is  decomposed  by  mineral  acids,  with  separation  of 
oily  drops  of  hydrogen  bisulphide  and  formation  of  strychnine 
salts. 

Brucine. — When  hydrogen  sulphide  is  passed  into  a  strong  solu- 
tion of  brucine  in  alcohol,  freely  exposed  to  the  air,  the  liquid  im- 
mediately assumes  a  yellow  colour,  and  after  a  time  deposits  yellow 
needles,  which,  on  prolonged  standing,  become  covered  with  a 
yellowish  red  layer  of  another  sulphur  compound.  The  yellow 
needles  gave  on  analysis  numbers  agreeing  with  the  formula 
C03  Hog  No  O4  Ho  So  +  2  Ho  0,  which  is  that  of  a  compound  of  1  mole- 
cule of  brucine  with  1  molecule  of  hydrogen  bisulphide.  This  for- 
mula, however,  is  of  no  value;  for  the  substance  after  drying  pos- 
sesses altered  properties,  and  its  composition  is  not  represented  by 


PHARMACEUTICAL    CHEMISTRY.  G7 

the  formula  Coj  H.,,  No  O4  Ho  So.  The  crystals  are  prismatic,  insoluble 
in  the  ordinary  solvents,  and  undergo  partial  decomposition  wlien 
kept.  They  are  decomposed  by  mineral  acids,  with  separation  of 
hydrogen  bisulphide  and  formation  of  brucine  salts.  The  melting 
point  is  about  125^. 

A  second  derivative  of  brucine  is  easily  obtained  by  passing  hydi'O- 
gen  sulphide  into  a  dilute  alcoholic  solution  of  the  alkaloid  (1  in 
100),  till  the  liquid  assumes  a  deep  yellow  colour,  and  allowing  it 
to  stand  in  loosely-covered  vessels.  In  the  course  of  twenty-four 
hours  there  is  formed  a  deposit  of  ruby  red  crystals,  which  after 
washing  with,  alcohol  and  ether  have  the  composition  represented 

by  the  formula  C03  Hog  No  0^     -    -.      The  ciystals  belong  to  the  tri- 

xdo  ou 

clinic  system.     In  their  behaviour  they  closely  resemble  the  foi'e- 
going  yellow  compound. 

The  formation  of  these  brucine  compounds  is  dependent,  like  that 
of  the  strychnine  compound,  on  the  presence  of  oxygen;  for  if  the 
air  be  perfectly  excluded  not  a  trace  of  them  is  produced.     The  fol- 
lowing equations  may  perhaps  represent  their  formation  : — 
a.  Hog  No  O4  +  2  Ho  S  +  0  =  Ho  0  +  C,  Ho^  N,  O4  H^  So ; 

Datermination  of  Mmnte  Q,uantities  of  Arsenic  Present  in  Mineral 
and  Organic  Substances.  M.  Crommydes.  \{BidL  Soc.  Chini.  [2], 
XXV.,  34S;  Journ.  Cheiii.  Soc,  July,  1876.)  The  author  considers  all 
the  methods  usually  employed  in  the  determination  of  small  amounts 
of  arsenic  to  be  inconvenient  or  inaccurate  ;  and  gives  the  prefer- 
ence to  the  method  first  proposed  by  Gautier,  which  consists  in 
evolving  the  arsenic  from  a  Marsh's  apparatus  in  the  form  of 
arseniuretted  hydrogen,  and  weighing  the  metallic  arsenic  obtained 
in  the  combustion-tube.  As  evidence  of  the  extreme  accuracy  of 
this  method,  the  following  results  are  given.  Orpiment  of  absolute 
purity  was  taken  : — 


C.  H,«  N,  O4  +  4  H,  S  +  0.  =  2  Ho  O  +  Co.  Ho„  No  _ .  .  ,_ 


Weight  of  Orpimeut 

Metallic  Arsenic 

iletallic  Arsenic 

taken. 

found. 

calculated. 

0-0108     . 

0-0065 

0-00658 

0-0052     . 

0-0330 

0-00308 

On  determining  the  arsenic  in  a  portion  of  the  same  sample  of 
orpiment,  by  the  ammonium-magnesium  arsenate  method,  inaccurate 
results  were  obtained,  as  will  be  seen  from  the  following  : — 


Orpiment 

Ammonium-macrnepium 

Arsenic 

Arsenic 

taken. 

Arsenate  obtained. 

found. 

calculated 

0-55 

0-8755 

0-314 

0-3353 

68 


YEAR-EOOK    OF    PHARMACY. 


Gautier's  method  is  equally  accurate  M-ben  applied  to  the  determi- 
nation of  arsenic  contained  in  large  quantities  of  organic  matter. 
Known  vohimes  of  a  standard  orpiment  solution  (05  gram  of  orpi- 
ment  dissolved  in  1  litre  of  water)  were  introduced  into  100  grams 
of  meat,  and  the  amount  of  arsenic  determined.  The  results  are 
criven  below : — 


Weight  of  Meat 
taken. 

C.C 

of  Solution 
taken. 

Weicrht  of 
Orpiment. 

Wei 

prht  of  Arsenic 
obtained. 

Arsenic 
calculated 

100  grams 

5              . 

0-0025 

. 

0-0015 

0-00152 

100     „ 

. 

10 

0-0050 

0.0030 

000301 

100     „ 

, 

5 

0-0025 

, 

0-0015 

0-00152 

It  is  necessary,  however,  to  abstain  from  carrying  on  the  carboni- 
zation of  the  organic  matter  too  far,  as  it  is  found  that  the  greater 
part  of  the  arsenic  remains  in  the  charcoal  as  sulphide.  In  order 
to  be  quite  certain  that  all  the  arsenic  is  in  solution,  the  organic 
matter  which  has  been  successively  treated  with  nitric  acid,  sul- 
phuric acid,  and  again  with  nitric  acid,  is  calcined  ;  the  residue  again 
treated  with  a  small  quantity  of  nitric  acid  ;  and  the  solution  evapo- 
rated down,  but  not  calcined.  By  this  process  all  the  arsenic  is 
obtained,  and  no  sulphide  remains  in  the  charcoal. 

Crystallized  Hydrobromate  of  Conine.  M.  M  our  rut.  (Bi'per- 
tolre  lie  Fhrnn.,  1871.5,  3G9.)  Of  the  various  salts  of  conine  the 
hydrobromate  is  the  one  most  easily  obtainable  in  a  crystallized 
state.  The  salts  prepared  from  the  ordinaiy  brown  conine  are 
generally  contaminated  with  a  brownish  black  substance,  which 
cannot  be  completely  removed  without  great  difficulty  and  loss. 
The  German  conine,  which  is  nearly  colourless,  presents  no  such 
difficulties,  and  yields  crystals  of  the  pure  hydrobromate  on  being 
mixed  with  dilute  hydrobromic  acid.  The  latter  is  added  to  the 
alkaloid  drop  by  drop  until  the  mixture  has  a  slight  acid  reaction, 
when  the  salt  begins  to  crystallize  out  in  the  foi-m  of  colourless 
prismatic  needles,  which  are  very  soluble  in  water  but  less  readily 
so  in  ether  and  chloroform.  They  fuse  at  100°  C.,  but  at  a  higher 
temperature  they  are  decomposed,  giving  off  the  odour  of  conine. 
By  the  careful  evaporation  of  the  liquor  at  a  gentle  heat,  a  large 
yield  of  crystals  can  be  obtained. 

Hydrobromate  of  conine  has  been  administered  with  success  to 
children  suffering  from  whooping  cough,  in  frequently  repeated 
iloses  of  two  to  five  milligrams  each.  The  subcutaneous  injection  of 
five  milligrams  of  the  salt  is  recommended  by  Dr.  Rcgnault  for  the 
relief  of  sciatica. 

Test  for   Sperm  Oil.    W. Gilmour.    (PJiarm.  Jourv.,  3rd  series. 


PHARMACEUTICAL    CHEMISTRY. 


GO 


vii.,  321).)  The  process  recommended  is  as  follows  : — Take  one  part 
by  weight  of  sulphuric  acid,  sp.  gr.  1"84,  to  four  parts  of  oil,  and  mix 
thoroughly.  Let  it  stand  for  about  twenty  minutes,  shaking  once  or 
twice  in  the  interval,  and  then  add  about  three  ounces  of  distilled 
water.  On  now  shaking  the  mixture  a  very  thick  saponaceous-like 
compound  will  be  formed,  which  should  be  throughout  of  uniform 
colour,  showing  that  the  mixture  is  complete.  After  letting  this  stand 
for  about  eight  hours,  it  will  be  found  to  have  separated  into  two  lay- 
ers, the  one  underneath  being  clear  and  colourless,  and  the  one  above 
a  dark  brown  viscous  mass,  in  which  the  cetin,  if  present,  will  be 
found  floating,  giving  it  a  mottled  appearance.  It  should  now  bo 
set  aside  for  a  further  interval  of  eight  or  twelve  hours,  so  that  all 
cetin  may  separate ;  on  which  it  should  be  transfex'red  to  a  larger 
vessel  containing  three  or  four  times  its  volume  of  water,  and  the 
whole  thoroughly  shaken.  The  cetin  will  now  be  found  floating  on 
the  surface  of  the  liquid,  and  should  be  filtered  out  and  thorougly 
washed  until  the  filtrate  ceases  to  have  a  milky  appearance,  and  then 
dried  spontaneously.  As  thus  obtained,  the  cetin  is  light,  ci'ystalline, 
pearl-white,  not  unlike  quinine  in  appearance,  but  more  glistening, 
and  has  neither  taste  nor  smell.  According  to  Christison,  it  is  a 
pure  proximate  principle,  intermediate  between  wax  and  the  con- 
crete oils,  and  presenting  all  the  leading  properties  of  spermaceti, 
but  less  greasy,  and  fusible  only  at  the  higher  temperature  of  120°. 
It  undergoes  partial  saponification  when  boiled  with  caustic  potash 
solution,  forming  a  brittle  soap  only  in  pai-t  soluble  in  water,  and 
composed  cbiefly  of  palmitate  of  potash,  oleate  of  potash,  and  a 
crystalline  principle  called  ethal. 

The  following  table  gives  the  amount  recovered  from  one  ounce 
by  weight  of  ten  different  samples,  with,  the  specific  gravity  of  each 
oil  respectively  : — 


Sample. 
1 

Sp.  Gr.  60'  F. 
•88-4 

Cetin  in  grains 
16-2 

2 

•880 

15-5 

3 

•886 

11^ 

4 

•383 

7  1 

5 

•881 

6^5 

6 

•884 

6' 

7 

•889 

4-2 

8 

•883 

B- 

9 

•882 

none. 

10 

£ • 

1  .       1. 

•896 
1            J 

J    -1 

J 

none. 

1 

All  the  foregoing   oils   have  been   tested  in  the  manner  indicated 


70  YEAR-BOOK   OF   PHARMACY. 

more  than  once  (in  most  instances  repeatedly)  Avith  nearly  uniform 
results,  so  that  it  appeal's  reasonable  to  assume  the  utility  of  tliis 
mode  of  determining  their  purity. 

The  author  has  endeavoured  to  extract  the  spermaceti,  previously 
known  by  this  means  to  be  present  in  some  of  these  oils,  by  boiling 
in  rectified  spirit  and  subsequent  crystallization.  Spermaceti,  it  is 
well  known,  is  soluble  in  boiling  rectified  spirit,  whilst  sperm  oil 
is  not ;  yet  every  attempt  thus  to  extract  the  spermaceti  failed ;  but 
whether  from  some  adulterations  of  these  oils  with  other  oils  soluble 
in  rectified  spirit,  or  from  other  impurities  still,  or  from  some  defect 
in  the  manipulation,  the  author  has  been  unable  to  determine.  It 
shows,  however,  not  only  how  prevalent  adulteration  is  in  this  valu- 
able oil,  but  also  how  defective  the  means  are  for  its  detection,  when 
dealers  in  every  case  prudently  refrain  from  giving  any  opinion  on 
its  purity,  and  when  further,  it  is  Jnioiun  that  the  annual  consumption 
is  much  in  excess  of  the  amount  actualhj  imported.  In  circumstances 
such  as  these  the  test  may  prove  of  much  practical  utility  to  those 
engaged  in  examinations  of  this  hind. 

Cresotic  Acid  and  Sodium  Cresotate.  Dr.  C.  F.  Beiss.  {New 
Remedies,  from  Pharm.  Ceniralhalle,  1876,  273.)  The  fact  that 
cresotic  acid  is  homologous  with  salicylic  acid  leads  the  author  to 
the  supposition  that  its  therapeutic  action  might  likewise  be  similar. 
The  results  of  his  experiments,  especially  in  cases  of  fever,  leave 
no  doubt  that  cresotic  acid  is  a  most  efiective  antipyretic  remedy, 
cori'esponding  in  its  actions  to  quina  or  to  salicylic  acid.  Sodium 
cresotate  was  administered  in  doses  of  6  to  8  grams.  After  its 
administration  the  patients  sometimes  complained  of  a  bad  taste, 
but  never  of  disagreeable  sensations ;  sometimes  it  produced  hum- 
ming in  the  ears,  but  very  rarely  hardness  of  hearing  after  a  few 
hours. 

Cresotic  or  carbocresylic  acid,  CgHgOa,  is  derived  from  cresol  or 
cresyl-alcohol  (CVHg^O),  inthesame  way  as  salicylic  acid  (C7H6  0a) 
is  from  phenol  or  phenyl-alcohol  (C,jH^  0),  by  passing  carbonic  acid 
gas  into  cresol  (or  phenol)  containing  metallic  sodium.  The  cresotic 
acid  crystallizes  from  its  hot  watery  solution  in  colourless  prisms. 
It  is  sparingly  soluble  in  cold  water,  readily  in  ether,  alcohol,  and 
alkaline  solutions.  Ferric  chloride  produces  the  same  violet  color- 
ation as  with  salicylic  acid.  Comparative  exjieriments  will  have 
to  be  made  to  determine  which  of  these  two  acids  has  stronger 
antipyretic  powers. 

Determination  of  the  Impurities  in[Nitre.  Prof.  R.  Fresenius. 
(Zeitschr.fii.rAnuhjt.-Cherii.,  187C,  G8 ;  Jmirn.  Chem.  Soc,  1870,  651.) 


PHAUMACEUTICAL    CHEMISTRY.  71 

As  chemists  are  frequently  required  to  determine  the  traces  of 
foreign  salts  in  different  kinds  of  purified  saltpetre,  the  author  pub- 
lishes a  method  of  procedure,  which  from  long  experience  he  has 
found  to  give  the  most  accurate  results. 

1.  Deter mlnatw)i  of  the  Water. — This  is  done  in  the  usual  way,  by 
ascertaining  the  loss  on  heating  a  weighed  portion  in  a  platinum 
crucible.  The  temperatui'e  may  be  gradually  raised  until  the  salt 
just  begins  to  melt. 

2.  Determination  of  the  CJilorine  and  of  the  Residue  insoluble  in 
Water. — 100  grams  ai-e  dissolved  in  hot  water,  and  the  residue 
collected  and  weighed  on  a  tared  filter.  The  filtrate  is  acidified 
with  pure  nitric  acid,  mixed  with  silver  nitrate,  and  kept  for  some 
time  in  the  dark  at  a  gentle  heat.  The  precipitate  is  then  collected 
on  a  small  filter,  and  determined  either  directly  as  silver  chloride, 
or  by  reduction  to  metallic  silver. 

3.  Determination  of  the  Lime,  Magnesia,  and  Soda. — 100  grams  of 
salt  are  dissolved  with  1'.5  gram  of  potassium  chloride,  in  about 
100  c.c.  of  water  ;  the  solution  is  then  mixed  with  about  500  c.c.  of 
pure  alcohol  of  9G  per  cent.,  well  stirred,  and  the  crystalline  residue 
separated  by  filtration  and  washed  with  alcohol.  The  filtrate  is 
then  evaporated  to  dryness,  the  residue  dissolved  in  a  little  water, 
and  the  solution  treated  as  before  with  alcohol,  and  filtered.  This 
having  been  again  repeated,  an  alcoholic  solution  is  obtained  con- 
taining all  the  lime,  magnesia,  and  soda,  but  only  a  small  quantity 
of  potassium.  This  solution  is  now  evaporated  to  dryness,  and  the 
residual  salts  converted  into  chlorides  by  digestion  with  hydrochloric 
acid,  after  which  the  lime  can  be  separated  by  ammonium  oxalate, 
and  the  magnesia  by  ammonium  phosphate.  The  filtrate,  freed  from 
lime  and  magnesia,  is  now  heated  in  a  platinum  basin  to  expel 
ammonia,  one  or  two  drops  of  ferric  chloride  added,  and  afterwards 
ammonia  or  ammonium  carbonate,  to  slight  alkaline  reaction ;  the 
liquid  is  then  warmed,  the  basic  phosphate  of  iron  filtered  ofi",  and 
the  filtrate  evaporated  to  dryness,  and  heated  until  the  ammonium 
salts  are  expelled.  From  the  residue  the  potassium  is  separated  as 
potassio-platinic  chloride,  together  with  the  excess  of  the  platinum 
salt,  decomposed  by  careful  heating  in  a  stream  of  hydrogen  gas. 
Finally,  the  sodium  chloride  is  extracted  with  water,  the  solution 
evaporated  to  dryness,  and  the  sodium  calculated  from  the  weight 
of  the  residue. 

An  actual  analysis  gave  : — 

[v>'0,         Xa>r03        Mg(X03).,        CaCXOj);        Na  C!        Insoluble.      Moisture. 
yU-8r24         0-0207  0-0093"         0-0006  '      0-0134        0-0210         0-1226  =  100 


72  YEAR-BOOK    OF    PHARMACY. 

Reactions  of  Carbolic,  Benzoic,  and  Salicylic  Acids.  Dr.  R. 
Godef  froy.  (Abstracted  from  the  Zeitschr.  des  oesterr.  AixAh.  Fe>*., 
in  Xev:  li em  edits.) 

Reactions  of  Carbolic  Acid. 

1.  Solutions  of  caustic  alkalies  dissolve  phenol  readily,  with  form- 
ation of  pheuates  (carbolates)  of  alkali  metals. 

2.  On  treating  phenol  with  an  excess  of  fused  caustic  potassa,  a 
copious  disengagement  of  hydrogen  gas  occurs  after  a  short  time ; 
■while  at  the  same  time  there  are  formed  oxybenzoic  and  salicylic 
acids  and  diphenol. 

3.  Potassium  or  sodium  dissolves  in  melted  phenol,  with  disen- 
gagement of  hydrogen  and  formation  of  phenate  of  the  alkali  metal. 

4.  On  passing  dry  carbonic  acid  into  phenol  containing  sodium 
in  solution,  sodium  salicylate  is  formed,  together  with  paraoxybenzoic 
acid. 

5.  Pieces  of  caustic  potassa  brought  into  a  solution  of  phenol  in 
chloroform  became  covered  with  a  rose  red  shell,  but  the  mixture 
soon  became  very  hot,  dark  coloured,  and  thick. 

On  adding  to  an  aqueous  solution  of  phenol  a  little  potas.sa, 
evaporating  to  dryness,  and  after  the  residue  has  become  cold,  pour- 
ing over  it  some  chloroform,  a  magnificent  purple  colour  makes  its 
appearance,  which  is  ascribed  to  the  formation  of  rosolic  acid. 
(J.  Guareschi,  Gaz.  Cliim.  Ifal,  3,  402.) 

6.  A  watery  solution  of  jihenol  immediately  discolours  potassium 
permanganate.  If  the  latter  be  added  until  the  colour  ceases  to 
disappear,  the  products  of  oxidation  are  only  carbonic  and  oxalic 
acids ;  if,  however,  the  oxidation  remains  incomplete,  the  products 
are  a  resin,  closely  allied  iu  composition  to  phenol,  a  small  quantity 
of  oxalic  acid,  and  a  few  other  bodies. 

7.  Strong  hydrochloric  acid  is  poured  upon  potassium  chlorate  in 
a  test  tube,  so  that  the  fluid  stands  a  few  centimetres  over  the  salt ; 
after  the  subsidence  of  the  first  reaction,  and  the  removal  of  the 
chlorine  vapours  from  the  upper  portion  of  the  test-tube  by  blowing, 
the  liquid  is  diluted  Avith  1^  volume  of  water;  water  of  ammonia 
is  now  poured  into  the  test-tube,  so  that  the  latter  forms  a  separate 
layer  over  the  other.  On  adding  to  this  test  liquid  a  watery  solu- 
tion of  phenol,  the  ammoniacal  layer  as.sumes  a  tint,  varying  with 
the  quantity  of  phenol,  from  rose  red,  through  blood  red,  reddish, 
or  dark  brown.  One  part  of  phenol  may  be  easily  recognised  in 
12,000  parts  of  liquid.     (Ch.  Rice,  Ainer.  Journ.  Pharm.,  1873,  98.) 

8.  On  pas.sing  the  vapour  of  phenol  over  zinc  in  powder,  benzol 
and  zinc  oxide  are  formed  :  2  Ce.  H.,  O  H  +  Zn„  =  2  Zn  0  -»•  2  d  Ua. 


PHARMACEUTICAL   CHEMISTRY.  73 

0.  On  adding  an  excess  of  bromine  -svater  to  a  dilute  aqueous 
solution  of  phenol,  there  is  immediately  formed  a  yellowish  white 
flocculent  precipitate  of  tribromphenol,  C^  H^  Br^  0  H.  This  reaction 
is  said  to  be  distinguishable  in  a  dilution  of  1  in  43,700,  and  by 
waiting  a  few  hours,  even  in  one  of  1  in  54,600  pax'ts. 

10.  On  shaking  a  watery  solution  of  phenol  with  aqueous  ammonia, 
and  exposing  the  liquid  to  the  vapour  of  bromine,  the  liquid  assumes 
a  distinct  blue  colour,  even  in  presence  of  only  T7xr-Juxi^^i  P^^'t  of 
phenol.     (F.  A.  Flilckiger,  Arcliiv  der  Pliarm.  [3],  3-30.) 

11.  Ou  mixing  a  solution  of  a  hypochlorate  with  ammonia  and  a 
liquid  containing  phenol,  an  intense  blue  colour  is  developed.  Very 
small  quantities  of  phenol  may  be  detected  by  this  i-eaction. 

12.  Dilute  solutions  of  phenol  are  coloured  violet  by  neutral 
aqueous  ferric  chloride  solution.  Alcoholic  ferric  chloride  solution 
produces  a  blue  colour  with  alcoholic  phenol  solution.  Free  acids 
prevent  the  reaction. 

13.  A  watery  solution  of  phenol  reduces  metallic  mercury  from  a 
solution  of  mercurous  nitrate,  and  the  liquid  assumes  a  red  colour, 
which  is  said  to  be  visible  still  if  only  7,  ooooth  part  of  phenol  is 
present. 

14.  By  united  action  of  iodine  and  mercuric  oxide  upon  phenol, 
substitution  products  of  the  latter,  containing  iodine,  are  foi-med. 
(P.  Weselsky,  Wien.  Ber.,  09,  ii.,  832.) 

15.  Albumen  is  immediately  coagulated  by  phenol. 

16.  Concentrated  sulphuric  acid  dissolves  phenol  without  colour, 
and  produces  phenol  sulphuric  (sulpho-carbolic,  sulphophenic)  acids. 
Warmed  with  fuming  sulphuric  acid,  phenol  yields  pheno-disulphuric 
acid,  which  latter  imparts  a  ruby  colour  to  ferric  chloride  solution. 

17.  On  heating  phenol  with  oxalic  and  sulphuric  acids  a  beautifully 
red  mass  is  obtained,  which  assumes  a  magnificent  purple  shade 
with  alkalies.     This  is  owing  to  the  formation  of  coraline. 

18.  On  heating  phenol  with  sublimed  (and,  therefore,  dehydrated) 
oxalic  acid  to  110°-120°  C,  rosolic  acid  is  formed.  ("  Prud'homme," 
Monit  Sclent.  [3],  3890.) 

19.  Nitric  acid  acts  upon  phenol  with  more  or  less  violence, 
depending  upon  its  concentration,  and  produces  mononitrophenol, 
C6H4(NO,)OH,  or  dinitrophenol,  CeH,(N  0,),  0  H,  or  trinitro- 
phenol,  Cg  Ho  (N  0)3  0  H.  This  latter  is  commonly  known  as  picric 
acid. 

Reactions  of  Benzoic  Acids. 
1.  On  passing  the  vapour  of  benzoic  acid  over  faintly  ignited  zinc 
powder,  essential  oil  of  bitter  almonds  is  formed.     (Baeyer.) 


74  ■  YEAR-BOOK    OF    PHARMACY. 

2.  Benzoic  acid,  heated  in  a  retort  with  coarsely  ground  pumice 
stone,  splits  into  benzol  and  carbonic  acid.  If  overheated,  carbon  is 
separated  and  naphthalin  and  pjrogcnic  oils  arc  formed.  (Barreswil 
and  Bondault.) 

3.  On  heating  benzoic  acid  with  a  mixture  of  acid  .sodium  sulphate 
and  sodium  chloride  to  200"  C,  there  arc  formed  benzyl  chloride, 
hydrochloric  acid,  and  normal  sodium  sulphate.     (BeketoiF.) 

4.  Benzoic  acid  is  soluble  in  solution  of  sodium  phosphates,  which 
give  up  to  it  1  or  2  atoms  of  sodium,  producing  thereby  sodium 
benzoate.  The  solutions  have  an  acid  reaction,  and  give  up  benzoic 
acid  on  evaporation,  or  to  ether.     (J.  Donath.) 

5.  On  mixing  3  molecules  of  benzoic  acid  with  1  molecule  of  glu- 
cose, and  heating  with  a  large  excess  of  strong  sulphuric  acid,  the 
liquid  assumes  a  fine  blood  red  colour,  which  disappeai's  after  a 
while  ;  finally  the  mass  turns  brown  and  black. 

6.  Aqueous  chromic  acid,  or  potassium  chromate  and  sulphuric 
acid,  do  not  alter  benzoic  acid  ;  no  odour  of  oil  of  bitter  almonds  is 
developed,  and  the  chromic  acid  is  not  reduced  (distinction  from 
cinnamic  acid). 

7.  A  neutral  solution  of  ferric  chloride  produces  in  neutral  solu- 
tions of  benzoates  a  flesh  coloured  precipitate  of  ferric  benzoate, 
insoluble  in  water  and  acetic  acid,  bat  decomposed  by  hydrochloric 
acid,  which  produces  free  benzoic  acid  and  ferric  chloride. 

8.  Silver  nitrate  produces  no  precipitate  iu  a  solution  of  benzoic 
acid  ;  but  on  saturating  the  free  acid  with  ammonia  a  white  crystal- 
line precipitate  of  silver  benzoate  is  immediately  produced.  This  is 
soluble  in  ammonia,  acetic  acid,  and  hot  water. 

9.  Mercurous  nitrate  produces  in  a  solution  of  benzoic  acid  a 
white  crystalline  precipitate  of  mercurous  benzoate,  veiy  difficultly 
soluble  in  water.  Alkaline  benzoates  produce  a  voluminous  non- 
crystalline precipitate. 

Head  ions  of  Salicylic  Acid. 

1.  Salicylic  acid,  heated  above  its  melting  point,  splits  into  car- 
bon dioxide  and  phenol :  — 

C7H«0:,-CO,  +  C«HcO. 

2.  On  distilling  salicylic  acid  witli  excess  of  lime,  calcium  car- 
bonate is  formed  and  phenol  distils  over : — 

C,  He  O,  +  Ca  0  =  Ca  0  0^  +  C«  II«  0. 

3.  If  salicylic  is  heated  with  amylic  alcohol  (fusel  oil)  under 
pre.ssure  at  2-50^  C,  it  .splits  likewise  into  carbon  dioxide  and 
phenol. 


PHARMACEUTICAL    CHEMISTRY.  To 

4.  Sodium-amalgam,  acting  upon  an  acidulated  solution  of  sali- 
cylic acid,  which  must  bo  coustautlj  kept  acid,  transforms  it  into 
salicjlous  acid : — 

C,  Hs  O3  +  H,  =  C7  H,,  0,  +  H,  0. 

5.  Sulphuric  acid  dissolves  salicylic  acid  without  colour,  and  forms 
from  it  two  isomeric  sulpho-salicylic  acids. 

G.  On  heating  salicylic  acid  with  dilute  sulphuric  acid  and  man- 
ganic oxide,  formic  acid  is  produced  which  may  be  distilled  off. 

7.  Dilute  sulphuric  acid  and  potassium  chromate  likewise  convert 
salicylic  acid  into  formic  and  carbonic  acids.      (Kraut.) 

8.  On  heating  a  mixture  of  sulphuric  acid,  wood  spirit  (methyl 
alcohol),  and  salicylic  acid,  an  agreeably  aromatic  liquid  distils  ovei% 
which  is  methylic  salicylate. 

9.  Concentrated  nitric  acid  converts  salicylic  acid  at  the  common 
temperatui'e  into  nitriosalicylic  acid,  C7  il^  (IST  0^)  0;; ;  dilute  nitric 
acid  produces  the  same  result  by  heating. 

10.  Fuming  nitric,  or  a  mixture  of  concentrated  nitric  and  sul- 
phuric acids,  converts  salicylic  acid,  under  violent  reaction,  into 
picric  acid,  Cg  H3  (N  0^)3  0,  and  carbonic  acid. 

11.  Chlorine  and  bromine  produce  substitution  products. 

12.  Iodine  acts  upon  a  watery  solution  of  the  acid  only  when 
heated  ;  if  melted  with  dry  salicylic  acid  it  produces  iodized  substi- 
tution products  and  a  red  amorphous  body. 

13.  Warm  hydrochloric  acid  dissolves  considerable  quantities  of 
salicylic  acid ;  on  cooling  or  on  dilution  with  water  it  separates 
again  in  brilliant  white  fine  needles.     (Grodeffroy.) 

14.  Potassium  chlorate  and  hydrochloric  acid  convert  it  into 
chloranil  (tetrachlorchinon),  Cg  C14  0^. 

15.  On  heating  salicylic  with  aqueous  hydriodic  acid  to  280'^  C, 
phenyl ic  ether  and  carbonic  acid  are  formed. 

16.  On  distilling  it  with  phosphorus  pentachloride,  chloro- 
salicylchloride,  C7  H4  CI.2  0,  is  formed. 

17.  If  phosphorus  trichloride  be  added  to  a  mixture  of  salicylic 
acid  and  aniliu,  salicylanilide,  Cg  HgN  H.  (C7H5  0.,),  is  pi-oduced. 

IS.  Iodine  and  mercuric  oxide  acting  on  salicylic  acid  produce 
iodized  substitution  products.  (P.  Weselsky,  Wien.  Ber.  69,  ii., 
832.) 

19.  On  mixing  salicylic  acid  (3  molecules)  with  glucose  (1  mole- 
cule), pouring  over  them  a  large  excess  of  concentrated  sulphuric 
acid,  and  gently  warming,  a  fine  blood  red  colour  is  produced  ;  this 
colour  disappears  after  a  while,  and  the  mass  turns  brown,  and 
finally  black.     (T.  L.  Phipson,  Chem.  Neius,  28,  13.) 


76  YEAR-BOOK    OP    PHARMACY. 

20.  Caustic  potassa  solution  dissolves  salicylic  acid  readily  ;  the 
solution  soon  turns  brown  in  the  air. 

21.  "Watery  solution  of  salicylic  acid  and  its  salts  is  coloured 
intensely  violet  by  ferric  salts.  This  reaction  is  so  delicate  that 
Aug.  Vogel.  (Pharm.  Zeit.  f.  Eussl,  187(3,  398,  from  Neii.  Re}).f. 
Pharm.)  has  proposed  it  as  a  substitute  for  alkaline  sulphocyanides 
as  reagents  for  ferric  compounds.  In  strongly  acid  solutions,  how- 
ever, this  reaction  does  not  take  place.  H.  ^V'eiakc  employs  it  as 
an  indicator  in  alkalimetry.  (W.  Weith,  Ber.  der  deiUsch.  Chem.- 
Ges.,  18G6,  342  ;  Neio  liemedics  v.,  137.) 

On  evaporating  the  intensely  violet  solution  containing  salicylic 
acid  and  ferric  salt  to  dryness,  the  colour  disappears  entirely  ;  but 
the  least  quantity  of  water  restores  it.      (Godeffroy.) 

22.  Salicylic  acid  mixed  with  cupric  sulphate  and  caustic  soda 
solution  produces  a  solution  of  an  intensely  bluish  green  colour, 
from  which  even  a  large  excess  of  alkali  fails  to  precipitate  any 
cupric  oxide.     (Zeit.f.  Anal.-Chcm.) 

23.  Solution  of  sodium  salicylate  forms  a  grass  green  licj^uid  with 
cupric  sulphate  solution  (Hager,  Pharm.  Centralh.) 

24.  Silver  nitrate  produces  a  white  precipitate  in  solutions  of 
alkaline  salicylates,  but  no  precipitate  in  solution  of  salicylic  acid. 

25.  Lead  acetate  behaves  like  the  preceding. 

2G.  On  mixing  a  hot  saccharated  solution  of  simple  calcium  sali- 
cylate, Ca  (Cr-Hj  03)0,  obtained  from  calcium  carbonate  and  aqueous 
solution  of  the  acid,  with  a  boiling  solution  of  caustic  lime  in 
saccharine  water,  a  heavy  crystalline  precipitate  of  so-called  neutral 
calcium  salicylate,  Ca  Cy  H^  O.5,  almost  insoluble  in  water,  is  jiro- 
duced.     (Limpricht,  Organ.  Ghem.,  18G2,  i.)04.) 

27.  If  a  solution  of  salicylic  acid  is  boiled  with  a  solution  of 
potassium  ferrocyanide,  hydrocyanic  acid  is  produced,  and  the  liquid 
becomes  turbid.  This  reaction  is  very  delicate,  and  permits  the 
detection  of  very  small  quantities  of  salicylic  by  means  of  the  re- 
agents for  hydrocyanic  acid.     (Godeffroy.) 

28.  On  boiling  a  solution  of  salicylic  acid  with  a  solution  of 
potassium  permanganate,  the  characteristic  colour  of  the  latter  is 
immediately  destroyed,  and  carbonic  acid,  phenol,  and  brown  liy- 
drated  manganic  oxide  are  produced. 

Betulin.  U.  Hausmann.  (Licbir/'s  Annalen,  clxxxii.,  308-380.) 
The  author  has  obtained  this  substance  from  the  light,  corky  layer 
of  birch  bark  by  exliausting  it  with  boiling  water,  then  boiling  the 
e.xhausted  bark  with  alcohol,  precipitating  the  alcoholic  decoction 
by  an   alcoholic    solution  of   neuti'al  acetate  of  lead,  heating  the 


rHARMACEUTICAL    CHEMISTRY.  77 

mixture  again  to  the  boiling-  point,  filterino-,  removing  the  lead  from 
the  filtrate  by  carbonate  of  ammonium,  again  filtering-,  and  allowing 
to  cool.  A  crystalline  magma  of  impure  betulin  was  thus  obtained, 
which  was  purified  by  repeated  washing-  with  small  quantities  of 
ether  and  recrystallization  from  boiling  alcohol. 

Pure  betulin  forms  long,  colom-less,  inodorous,  and  tasteless 
7)risms,  which  when  dry  present  the  appearance  of  asbestos.  It 
fuses  at  258°  C,  and  when  heated  beyond  that  point  sublimes  in 
long,  very  thin  needles.  It  is  insoluble  in  water,  slightly  soluble  in 
cold  alcohol,  ether,  benzol,  and  chloroform,  and  freely  soluble  in  hot 
alcohol ;  also  in  glacial  acetic  acid,  oil  of  almonds,  and  turpentine. 
Its  composition  is  represented  by  the  formiila  C.,(,_  Hf.,,  O...  By  dry 
distillation  oily  products  are  obtained,  possessing  the  characteristic 
odour  of  russia  leather.  "With  acetic  anhydride  it  forms  betulin 
diacetate,  a  crystallizable  ether,  the  composition  of  which  agrees 
with  the  formula  Cjo  H^-j  0-.  With  nitric  acid  it  forms  betulin- 
amaric  acid,  C^j;  H-.^  O^^ ;  and  by  the  action  of  chromic  anhydride  it 
is  converted  into  betnlinic  acid,  C,^.  H-jO,.. 

Detection  of  Mineral  Acids  by  Colchicine.  Prof.  F.  A.  Fliick- 
iger.  {Jonrn.  CJiern.  Soc,  from  liejTerf.  Pharm.,  xxv.,  18.)  Mohr 
has  observed  that  under  certain  conditions  the  behaviour  of  inor- 
ganic acids  differs  totally  from  that  of  the  organic  acids  ;  this  differ- 
ence may  be  utilized  for  their  discovery  in  presence  of  organic  acids; 
for  example,  in  vinegar  or  lemon  juice. 

Potassium  sulphocyanate  in  a  dilute  solution  of  ferric  acetate 
causes  no  change,  but  if  there  be  the  smallest  trace  of  hydrochloric, 
nitric,  or  sulphuric  acid  present,  the  blood  red  colour  of  ferric  sul- 
phocyanate is  at  once  apparent ;  this,  however,  quickly  vanishes  on 
the  addition  of  an  acetate  or  oxalate ;  but  in  this  case  phosphoric 
acid  acts  like  the  organic  acids  in  preventing  the  formation  of  ferric 
sulphocyanate.  Another  of  Mohr's  methods  depends  on  the  fact 
that  iodine  is  precipitated  from  a  solution  of  potassium  iodide  if  a 
ferric  salt  with  an  inorganic  acid  radicle  be  added.  Ferric  acetate 
causes  no  precipitation  in  a  solution  of  potassium  iodide,  but  if  the 
smallest  trace  of  an  inorganic  acid  be  present  the  iodine  is  imme- 
diately precipitated. 

But  there  is  a  case  the  reverse  of  this,  in  which  the  inorganic  re- 
tards and  the  organic  acid  hastens  the  reaction.  A  soltition  of  pure 
ferrous  sulphate  mixed  with  a  saturated  solution  of  gallic  acid  pro- 
duces no  change  if  the  air  be  excluded,  but  acetates  immediately 
produced  in  it  a  violet  colour. 

Still  more  remarkable  effects  are  produced  by  colchicine.     Some 


78  YEAR-BOOK    OF    PHARMACY. 

colchicine  was  extracted  from  a  few  grams  of  the  seeds  by  means  of 
alcohol  and  water,  the  yellowish  solution  was  diluted  till  the  colour 
was  scarcely  perceptible. 

With  concentrated  sulphuric  or  nitric  acid  it  gave  a  very  distinct 
yellow,  and  on  adding  a  drop  of  hydrochloric  acid  to  this  solution  a 
bluish  violet  was  produced. 

If  some  colchicine  solution  with  a  drop  of  nitric  acid  is  strongly 
concentrated,  and  then  a  fragment  of  sodium  acetate  added,  an 
orange  colour  is  produced. 

If  to  a  portion  acidulated  with  sulphuric  acid,  a  mixture  of  iodide 
of  potassium  and  iodide  of  mercury,  in  the  proportion  of  i)0  to  13'5, 
is  added,  a  precipitate  is  formed.  By  means  of  this  solution  it  was 
easy  to  detect  half  a  jier  cent,  of  sulphuric  acid  in  vinegar. 

The  Detection  of  Mineral  Adulterants  in  Flour.  Dr.  C.  Hiraly. 
(Pharmaceutlsche  Handel shlatt,  Xo.  7G.)  As  the  complete  incinera- 
tion of  flour  is  a  somewhat  tedious  operation,  the  author  prefers  to 
effect  the  separation  of  mineral  adulterants  by  means  of  chloi-oform. 
Flour  being  much  lighter,  and  the  ordinary  mineral  adulterants 
(limestone,  chalk,  heavy  spar,  gypsum,  and  bone  ash)  much  heavier, 
than  chloroform,  a  sample  of  the  suspected  flour  need  only  be 
shaken  with  it  in  a  test-tube,  and  then  allowed  to  separate  A  very 
slight  dark  coloured  sediment,  emanating  from  the  millstone,  will 
be  deposited  from  a  genuine  flour,  but  any  appreciable  white  sedi- 
ment indicates  adulteration.  The  sediment,  of  course,  can  be 
weighed  and  further  examined. 

The  author  has  also  employed  this  process  for  the  separation  of 
•white  arsenic  from  a  sample  of  flour  in  a  forensic  investigation. 

Alteration  of  Cantharidin  in  Cantharides.  R.  Wolf  f.  (Zeitsch: 
lies  oestcr  Apoih.  Yer.,  xv.,  102;  PJiarm.  Jov.rn.,  3rd  series,  vii.,  918). 
The  experience  that  cantharides  kept  dry  remain  active  for  a  long 
time,  whilst  when  damp  they  rapidly  lose  their  activity ;  and  fur- 
ther, the  property  of  cantharidin  not  to  be  broken  up  under  the  action 
of  strong  sulphuric  acid,  whilst  in  the  cantharides  it  loses  almost 
directly  its  vesicatory  action  upon  the  skin,  led  the  author,  who  is 
an  apothecary  in  Buenos  Ayres,  to  the  conclusion  that  there  must 
be  present  in  cantharides  some  substance  which,  assisted  by  mois- 
ture, eflected  a  change  in  the  cantharidin.  As  it  is  known  that  there 
is  an  evolution  of  ammonia  when  an  aqueous  solution  of  old  canth- 
arides is  heated  with  caustic  potash,  the  opinion  appeared  to  be  justi- 
fied that  ammonia  might  play  an  important  part  in  the  decomposition 
of  the  cantharidin. 

To  clear  up  this  point  the  author  extracted  the  cantharidin  from 


PHARMACEUTICAL    CHEMISTRY.  79 

100  grams  of  Lytta  aspersa.  This  species  is  used  in  Buenos  Ayres, 
and  is  said  to  excel  the  ordinary  Lytla  vcsicatoria  in  its  greater 
activity,  which,  when  carefully  dried,  the  insects  retain  during  many 
years.  From  the  100  grams  he  obtained  0"815  gram  of  pure  cantli- 
aridin,  and  also  from  the  greeu-brown  oily  substance  from  which 
the  cantharidin  had  separated  upon  treating  it  with  ether  and  chlo- 
roform, 0'4G  gram  of  a  new  body  in  tabular  crystals,  which,  although 
it  also  had  a  vesicatory  action,  differed  from  cantharidin  in  its 
chemical  properties  as  well  as  its  form  of  crystallization. 

The  crystals  of  this  new  body  are  difficultly  soluble  in  cold  water 
(about  1  in  6600);  they  are  rather  more  soluble  in  boiling  water, 
but  separate  upon  cooling.  In  alcohol  they  dissolve  in  the  propor- 
tion of  1  in  080  ;  in  ether,  1  in  390  ;  in  chloroform,  1  in  60.  Hydro- 
chloric acid  is  without  action  upon  them ;  on  the  other  hand,  they 
are  readily  dissolved  by  nitric  and  sulphuric  acids,  especially  when 
hot.  In  the  latter  case,  however,  decomposition  appears  to  take 
place,  since  upon  the  addition  of  water  cantharidin  is  precipitated, 
ammonium  nitrate  or  sulphate  being  formed  at  the  same  time. 

When  pulverized  the  new  body  dissolves  at  the  ordinary  tempera- 
ture in  solution  of  potash  or  ammonia ;  and  upon  the  addition  of  an 
acid  is  again  precipitated  unaltered.  If  the  ammoniacal  solution  be 
allowed  to  stand  for  some  time  in  a  moderately  warm  place,  after 
the  excess  of  ammonia  has  been  given  off,  the  solution  readily  red- 
dens blue  litmus  paper.  If  the  ammoniacal  solution  be  concen- 
ti-ated,  crystals  of  the  compound  with  ammonia  are  formed,  which 
decompose  upon  drying,  with  formation  of  ammonia,  and  are  then 
difficultly  soluble  in  cold  water. 

Upon  evaporating  the  ammoniacal  solution  to  dryness  a  white 
crystalline  residue  is  obtained,  that  appears  to  be  insoluble  in 
cold  water,  but  in  boiling  water  it  dissolves  without  difficulty. 
From  the  solution,  which  reddens  litmus  paper,  acicular  crystals 
separate  upon  cooling,  ivhich  constitute  a  second  nitrogenous 
compound  of  cantharidin.  The  author  made  no  closer  inves- 
tigation as  to  the  composition  of  these  two  compounds.  In  the 
remainder  of  the  paper  he  simply  distinguishes  them  as  No.  1  and 
Xo.  2.  Compound  No.  2,  placed  on  the  skin,  acts  as  a  vesicant. 
It  dissolves  with  difficulty  in  cold  water,  but  readily  in  boiling 
water.  In  alcohol,  ether,  and  chloroform  it  is  very  difficultly  soluble, 
even  when  warmed.  In  acetic  ether  it  is  easily  soluble,  and  upon 
evaporation  cantharidin  is  left  as  a  residue.  The  crystals  dissolve 
readily  in  strong  sulphuric  acid,  and  no  precipitation  takes  place 
upon  the  addition  of  water.     Strong  nitric  and  hydrochloric  acids 


80  YEAR-BOOK    OF    niAKMACY. 

behave  similarly.  It  appears  as  if  the  acids  enter  into  combination 
■without  causing  decomposition.  In  ammonia  this  compound  No.  2 
dissolves  rather  freely,  but  separates  in  acicular  crystals  upon  the 
addition  of  acids.  If  the  ammoniacal  solution  be  allowed  to  evapo- 
rate slowly,  ci'ystals  are  formed  which  consist  of  compound  No.  2 
and  ammonia ;  upon  drying  and  warming,  these  crystals  are  decom- 
posed with  evolution  of  ammonia.  It  is  also  dissolved  by  potash 
solution,  but  it  then  separates  unaltered  upon  the  addition  of  acids. 
Upon  evaporating  the  solution  in  alkali  to  dryness,  ammonia  is 
evolved,  and  part  of  the  compound  No.  2  passes  into  compound 
No  1.  No.  2  appears  to  undergo  no  change  upon  fusion  or  sub- 
limation ;  No.  1  also  appears  to  melt  and  sublime  without  loss  of 
weight. 

If  solution  of  a  zinc  salt  be  added  to  solution  of  cantharidin  in 
caustic  potash  as  long  as  any  precipitate  is  foi'med,  then  a  suflficiency 
of  ammonia  solution  to  dissolve  the  precipitate  produced,  and  finally 
an  acid  in  excess,  the  compound  No.  I  separates  as  a  white  granular 
crystalline  precipitate.  Salts  of  copper  and  magnesia  act  like  the 
salts  of  zinc,  as  probably  do  others  that  behave  similarly  towards 
ammonia.  As  magnesia  salts  are  present  in  considerable  quantity 
in  cantharides,  the  author  is  of  opinion  that  these,  after  the  death 
of  the  insect,  in  presence  of  ammonia,  quickly  induce  an  alteration 
of  the  cantharidin  into  compound  No.  1,  and  that  this  change  is  more 
rapid  and  complete  in  proportion  as  the  conditions  are  favourable, 
which  appears  to  be  the  case  in  the  European  cantharides,  that  so 
soon  lose  their  activity.  If  by  moisture  a  progi'essive  formation  of 
ammonia  is  favoured,  the  compound  No.  1  is  formed,  and  this  after 
a  time  is  in  turn  converted  into  compound  No.  2,  which  then  pro- 
bably enters  into  combination  with  acids  contained  in  the  canthar- 
ides. The  author  has  no  doubt  that  a  more  exact  investigation  of 
the  nitrogenous  compounds  would  afford  a  method  of  recovering 
the  cantharidin  that  has  undergone  alteration  in  cantharides,  the 
details  of  which  would  vary  according  to  the  degree  of  change  that 
has  taken  place. 

Rhodeine,  a  New  Reaction  of  Aniline.  G.  Jacquemin. 
(Joura.  de  Phann.  et  de  Chiut.,  xxiv.,  204.)  Professor  Dragendorff 
has  shown  that  the  well-known  reaction  of  aniline  with  chlorinated 
lime  fails  to  indicate  this  substance  if  its  solution  contains  less  than 
1  in  GOOO.  A  few  years  ago  the  author  observed  that  by  substitut- 
ing sodium  hypochlorite  for  the  chlorinated  lime,  O'Ol  gram  of 
anilin  dissolved  in  100  c.c.  of  water,  or  1  in  10,000,  still  produces 
a  distinct  violet  coloration ;  whereas  solutions  containing  1  part  in 


PHARMACEUTICAL    CHEMISTRY.  81 

20,000  give  but  a  faiat  brown,  non-characteristic  colour  ;  and  those 
containing  1  part  in  50,000  undergo  no  visible  change  whatever.  He 
has  now  discovered  a  reaction  by  means  of  which  aniline  can  be 
distinctly  recognised  in  solutions  containing  1  part  in  250,000,  and 
Avhich  may  therefore  be  advantageously  employed  when  the  hypo- 
chlorite fails.  By  the  addition  of  a  few  drops  of  largely  diluted 
solution  of  ammonium  sulphide  (1  drop  to  30  c.c.  of  water)  to  the 
colourless  or  faintly  brown  mixture  of  aniline  solution  and  sodium 
hypochloi'ite,  a  beautiful  pink  coloration  is  produced,  which  is  still 
discernible  in  a  solution  containing  but  4  milligrams  of  aniline  per 
litre  of  water,  but  is  instantly  destroyed  by  an  excess  of  ammonium 
sulphate. 

The  author  hopes  to  isolate  and  to  further  investigate  this  new 
derivative  of  aniline,  to  which  he  has  given  the  name  rhodeine. 

Gentisin  (Gentianin).  H.  Hlasiwetz  and  J.  Habermanrt 
(Liehlr/s  Annalen,  clxxx.,343;  Journ.  Ghem.  Soc,  July,  1876.)  The 
author's  latest  researches  on  this  subject  establish  the  indentity  of 
pyrogentisic  acid  with  hydroquinone.  The  true  melting  point  of  the 
latter  is  169°.  Gentisic  acid  is  proved  to  be  identical  with  oxysalicy- 
lic  acid,  which  melts  when  pure  at  196°-197°. 

By  the  action  of  sodium  amalgam  upon  gentisin  a  body  is  formed 
having  the  formula  C;^^  H^^g  ^s?  which  differs  from  that  of  gentisin 
by  C  O.  Fusel  gentisin,  when  treated  with  dry  hydrochloric  acid, 
yielded  methylchloride.  Gentisin,  therefore,  contains  the  radical  C  H^. 
In  a  previous  paper  a  diacetyl-gentisin  was  described,  showing  the 
presence  in  gentisin  of  two  hydroxyl-groups.  These  facts  admit  of 
explanation  on  the  assumption  that  gentisin  is  formed  by  the  combi- 
nation of  phloroglucin  with  a  body  isomeric  with  piperonal,  thus : — 


Piperoual  isomer.  Phloroglucin.  Gentisin. 

(CH3 


G^B.J,  0 


CfiH.K  n  >         +  CfHg  ^OH-H,0  =  CO 
HCOH  (OH  -  I 


C,  H.  ^  Q  f 


Veratrine.  E.  Schmidt  and  R.  Kopper.  (From  I?er.  ^/er 
deutsch.  Chem.-Ges.,  ix.,  1115  ;  Journ.  Chein.  Soc,  jS'ov.,  187G,  530.) 
Crystallized  veratrine  was  prepared  by  the  authors  according  to  the 
directions  of  Merck,  partly  fi'om  commercial  verati-ine  and  partly 

G 


82  YEAR-BOOK   OP    PHARMACY. 

from  veratrine  made  by  themselves.  The  general  properties  of  the 
substance  accord  with  the  statements  of  Merck  and  Weigclin  re- 
specting it.  It  melts  at  205°.  The  numbers  obtained  by  analysis 
(64"63  per  cent,  carbon,  8'G8  per  cent,  hydrogen,  2GG  per  cent, 
nitrogen)  lead  to  the  formula  C.^^  H^q  N  Og.  The  hydrocliloride 
forms,  with  gold  trichloride,  the  compound  C.,.,  H^^  N  Oy  H  CI  + 
Au  CI3,  which  crystallizes  in  yellow  needles ;  with  platinum  tetra- 
chloride, an  indistinctly  crystalline  compound  (C;^2H5qNO,j  H  C1)o  + 
Pt  C\^  ;  and  with  mercuric  chloride,  a  Avhite  crystalline  precipitate, 
C32  H-o  N  O9  H  CI  +  Hg  Clo.  The  sulphate  (C32  H^q  N  Og)^  H.  S  0„ 
and  hydrochloride,  are  non-crystallizable. 

Crj^stallized  veratrine  is  insoluble  in  water,  but  on  pi'olonged 
washing  therewith  it  becomes  transformed  into  a  soluble  modifica- 
cation,  the  solution  of  which  leaves  when  evaporated  a  yellowish 
amorphous  mass  having  the  same  composition  as  the  crystals. 
Veratrine  dissolved  in  Avater  is  rendered  insoluble,  and  is  conse- 
quently precipitated,  by  heating  the  solution.  Acids  also  appear  to 
convert  the  soluble  into  the  insoluble  modification. 

Several  samples  of  commercial  veratrine  examined  by  the  authors 
were  found  to  be  almost  pure. 

Method  for  the  Analysis  of  Alkaline  Mineral  Waters.  Prof.  R. 
Presenius.  (C'Ae»i.6'cH^r., Nov.,  1870,549,  from  Ze'dschr.fur  Anahjt.- 
Cliem.,  XV.,  221-230.)  The  author  publishes  the  following  modified 
and  improved  process  for  the  complete  analysis  of  alkaline  and 
ferruginous  mineral  waters  : — 

1.  Determination  of  Chlorine,  Bromine,  and  Iodine  mixed. — About 
2000  grams  of  water  are  evaporated  on  a  water  bath  to  one-quarter 
of  its  original  bulk.  The  solution  is  filtered,  washed,  the  filtrate 
acidified  with  nitric  acid,  precipitated  with  argentic  nitrate,  and  the 
precipitate  weighed  either  as  such  or  after  ignition  in  a  stream 
of  hydrogen. 

2.  Determination  of  Silicic  Acid,  Iron,  Manganese,  Alumina, 
Lime,  and  Magnesia. — About  7000  grams  of  water  are  acidified  and 
evaporated  to  dryness  in  large  platinum  dishes.  The  residue  is 
moistened  with  hydrochloric  acid,  water  added,  the  solution  warmed, 
and  the  silicic  acid  filtered  ofi"  and  washed.  After  weighing,  the 
silica  is  ignited  with  ammonium  fluoride  and  sulphuric  acid.  Any 
non-volatile  substances  are  deducted.  The  silicic  acid  filtrate  is 
treated  with  ammonia,  and  the  precipitate  is  filtei'cd  after  warming, 
and  then  washed.  The  latter  (mostly  hydrated  ferric  oxide)  is  dis- 
solved in  hydrochloric  acid,  neutralized  with  ammonium  carbonate, 
boiled  and  filtered.      Should  ammonia   give  a  precipitate  in  the 


I 


PHARMACEUTICAL    CHEMISTRY.  bo 

filtrate,  it  is  filtered  separately,  dissolved,  and  reprecipitated.  The 
filtrates  are  put  togetlier.  The  two  precipitates  are  again  dissolved, 
the  solution  treated  with,  chemically  pure  alcohol  (free  from  alumina), 
ammonia  added,  and  the  iron  precipitated  with  ammonium  sulphide. 
Having  thus  separated  the  iron  from  the  alumina  and  the  phos- 
phoric acid,  the  ferrous  sulphide  precipitate  is  dissolved  in  hydro- 
chloric acid,  the  solution  oxidized  with  nitric  acid,  precipitated  with 
ammonia,  and  weighed  after  ignition  as  ferric  oxide.  The  filtrate 
from  the  sulphide  is  evaporated  to  dryness  in  a  platinum  dish,  -with 
addition  of  a  solution  of  sodium  carbonate,  and  the  residue  is  heated 
with  nitre.  After  moistening  with  water  it  is  dissolved  in  hydro- 
chloric acid,  and  the  solution  is  filtered  and  precipitated  with 
ammonia.  Traces  of  a  flocculent  precipitate  of  aluminum  phosphate 
are  generally  obtained.  The  filtrates  containing  the  manganese, 
lime,  and  magnesia  are  concentrated  ;  the  manganese  is  precipitated 
with  ammonium  sulphide  ;  the  precipitate,  after  2'i  hours,  collected 
in  a  filter,  redissolved  and  reprecipitated;  the  precipitate  mixed  with 
sulphur  and  ignited  in  a  stream  of  hydrogen ;  and  the  manganese 
weighed  as  sulphide.  The  filtrates  are  evaporated  with  hydrochloric 
acid,  the  sulphur  filtered  ofi",  and  the  lime  precipitated  in  the  filtrate 
with  ammonia  and  ammonium  oxalate.  The  precipitate  is  redissolved 
and  reprecipitated,  and  finally  weighed  either  as  carbonate  or  oxide. 
The  filtrates  are  evaporated  to  dryness ;  the  ammonia  salts  expelled 
by  ignition  ;  the  residue  is  moistened  with  hydrochloric  acid  and 
evaporated  to  dryness,  again  taken  up  with  hydrochloric  acid  and 
water ;  and  the  magnesia  is  precipitated  with  sodium  phosphate  and 
weighed  as  pyrophosphate. 

3.  Determination  of  the  Sttlphicric  Acid  and  tlic  All-alies. — About 
3000  grams  of  the  water  are  acidified  with  hydrochloric  acid,  evapo- 
rated, and  the  silicic  acid  filtered  off,  as  in  No.  2.  The  filtrate,  which 
must  not  contain  much  hydrochloric  acid,  is  precipitated  at  the  boil- 
ing heat  by  carefully  adding  barium  chloride.  The  precipitate  is 
first  weighed,  then  warmed  with  hydrochloi'ic  acid,  and  thoroughly 
washed.  The  solution  is  evaporated  to  dryness  with  a  few  drops  of 
barium  chloride  solution,  dissolved  in  water,  filtered,  and  the  pre- 
cipitate weighed  with  the  former.  The  last  weight  is  regarded 
as  the  more  accui'ate.  The  filtrate  is  evaporated  to  dryness,  the 
residue  taken  up  with  water,  and  the  solution  boiled  with  addition 
of  pure  milk  of  lime.  The  filtrate  is  precipitated  with  ammonium 
carbonate  and  oxalate.  The  filtrate  from  the  precipitate  is  evapor- 
ated to  di'yness,  the  ammonia  expelled  by  ignition  in  a  platinum 
dish,  and  the  separation  of  the  magnesia  repeated^  using  very  small 


84  •i'EAU-BOOK    OF    PHARMACY. 

quantities  of  the  reagents.  After  expulsion  of  the  ammonia-salts 
the  allcoliiie  chlorides  are  obtained.  In  order  to  separate  the  potas- 
sium chloride  from  the  sodiiim  and  lithium  chlorides,  all  three 
are  converted  into  platino-chlorides,  and  the  dry  precipitate,  after 
treatment  with  alcohol  of  80  volumes  per  cent.,  is  filtered  and  washed 
with  alcohol.  The  potassium  salt  having  been  transferred  to  a 
small  tared  platinum  capsule,  the  remainder  in  the  filter  is  dissolved 
in  boiling  water,  evaporated  to  dryness,  and  Aveighed  at  130°.  To 
test  the  purity  of  the  potassium-platino-chloride,  it  is  again  treated 
with  water,  platinum  chloride,  and  alcohol,  as  above  mentioned. 
The  last  weight  is  regarded  as  the  more  accurate.  The  quantity  of 
sodium  chloride  is  obtained  by  deducting  the  quantity  of  potassium 
chloride  and  lithium  chloride  (determined  by  the  method  described 
below)  from  the  total  sum  of  alkaline  chlorides.  Traces  of  alkaline 
earths,  if  present,  must  be  determined  and  deducted  from  the  total 
alkaline  chlorides. 

4.  Determination  of  the  Carhonic  Acid. — The  process  as  described 
in  Anleitimg  zur  quant.  Analyse,  6  Aufl.,  p.  436,  etc.,  is  used. 

5.  Determination  of  the  Solid  Residue. — About  500-1000  grams  are 
evaporated  in  a  tared  platinum  dish  on  a  water  bath,  and  the  resi- 
due is  dried  at  180°,  and  weighed.  It  is  treated  with  water  and 
hydrochloric  acid,  then  with  excess  of  sulphuric  acid,  evaporated 
to  dryness,  and  ignited  for  some  time  with  addition  of  solid  am- 
monium carbonate,  so  as  to  convert  the  acid  sulphates  of  the  alka- 
lies in  neutral  sulphates  (till  constant  in  weight).  The  solid 
residue  of  ferruginous  waters  is  best  determined  with  the  water  of 
bottles  into  which  the  iron  has  been  completely  deposited  as  hydrated 
ferric  oxide  by  the  action  of  the  air.  The  solution  is  filtered,  and 
the  filtrate  treated  as  in  the  preceding  case.  The  precipitate  is 
dissolved  in  nitric  acid ;  silicic  acid,  if  present,  is  determined  and 
added.  The  nitric  acid  solution  is  evaporated,  the  residue  ignited, 
treated  with  water  and  ammonium  carbonate,  then  heated  moder- 
ately, and  weighed ;  and  the  weight  is  added  to  that  obtained  by 
weighing  the  solid  residue  of  the  filtrate  at  180°.  The  ferric  oxide, 
etc.,  is  treated  with  nitric  and  sulphuric  acids,  evaporated  and 
ignited.     The  weight  obtained  is  added  to  the  weight  of  sulphates. 

6.  Determination  of  Iodine,  Bromine,  Lithium  (Manganese),  Ba- 
rium, and  Strontium. — About  GO  litres  are  evaporated  in  a  tinned 
copper  still  to  about  4  or  5  litres,  the  alkaline  liquid  is  filtered,  and 
the  residue  washed  with  hot  water  until  the  washings  are  free  from 
alkali.  The  residue  is  also  treated  until  a  lithium  line  is  no  longer 
visible  in  the  spectrum.      The  solution  (a)  serves  for  determining 


PHAEMACEUTICAL    CHEMISTRY.  85 

iodine,  bromiue,  and  lithium;  and  tlie  residue  (//)  for  determining 
the  (maDganese)  barium  and  strontium. 

(rt)  TJie  solution  is  evaporated  and  alcohol  (95  per  cent.)  atlded, 
with  constant  mixing  ;  the  filtered  residue  is  boiled  three  times  with 
the  alcohol,  and  the  alcoholic  solution  is  distilled  over,  with  addi- 
tion of  two  drops  of  strong  potash  ley.  The  residue  is  dissolved  in 
water,  evaporated,  and  again  treated  with  alcohol  of  9G  per  cent. 
The  solution  is  redistilled,  and  the  residue  again  treated  as  above. 
An  alcoholic  solution  is  thus  obtained  which  contains  all  the  iodine 
and  bromine,  but  only  traces  of  alkaline  chloride.  The  solution  is 
evaporated  in  a  platinum  dish  with  addition  of  two  drops  of  potash, 
ley,  and  the  residue,  after  gentle  ignition,  is  extracted  with  boiling 
water.  If  the  solution  be  coloured  brownish  it  is  again  evaporated 
with  two  drops  of  potash  ley  and  a  small  quantity  of  nitre,  and  the 
residue  is  again  heated  moderately.  The  solution,  now  colourless, 
is  treated  with  carbon  bisulphide,  and  acidified  with  dilute  sulphuric 
acid;  a  small  quantity  of  a  solution  of  nitrous  acid  in  sulphuric 
acid  is  then  added,  with  agitation,  and  the  violet  coloured  carbon 
disulphide  is  washed  out. 

The  iodine  is  determined  in  this  liquid  with  a  very  dilute  solu- 
tion of  sodium  thiosulphate.  From  the  solution  left  after  washing 
out  the  iodiferous  carbon  disulphide,  bromine  and  chlorine  ai-e  pre- 
cipitated in  the  form  of  silver  compounds,  and  the  bromine  is  de- 
termined by  deducting  the  weight  obtained  by  heating  weighed 
quantities  of  the  bromo-chloride  of  silver  in  a  stream  of  chlorine. 
The  filtrate  from  the  silver  compounds  is  treated  with  hydrochloi'ic 
acid,  and  filtered,  and  the  filtrate  is  set  aside. 

For  the  determination  of  lithium  (1),  the  three  residues  lefc  by 
the  treatment  with  alcohol  (2),  the  two  incinerated  filters  through 
which  the  solution  (free  from  organic  matter)  of  the  alkaline 
metals  was  filtered,  and  (3)  the  solution  which  was  obtained  after 
separating  the  excess  of  silver  are  used.  The  three  are  mixed 
together  with  water,  and  then  hydrochloric  acid  is  added,  and  the 
solution  evaporated.  The  residue  is  treated  with  absolute  alcohol 
and  filtered,  and  the  residue  is  boiled  with,  small  quantities  of 
strong  alcohol,  until  either  the  residue  of  sodium  chloride,  or  the 
evaporated  residue  of  the  last  alcoholic  extract  no  longer  gives  a 
lithium  spectrum.  The  alcoholic  filtrates  are  distilled  off,  the  resi- 
due dissolved  in  water,  with  addition  of  two  drops  of  hydrochloric 
acid,  the  solution  is  evaporated,  and  the  treatment  with  absolute 
alcohol  twice  repeated,  adding  to  the  last  alcohol  used  half  its  volume 
of  ether,  and  always  testing  the  residues  by  the  spectrum.      The 


8Q  YEA.E-BOOK    OF    PHARMACV. 

ethereal-alcoholic  solution  is  now  distilled  off;  the  residue  moistened 
with  -water ;  hydrochloric  acid  added ;  the  liquid  again  evaporated 
to  dryness;  the  residue  taken  up  with  -water;  and  to  remove  small 
portions  of  phosphoric  acid  -n'hich  may  have  gone  over  into  the 
solution,  two  drops  of  iron  solution  are  added.  Pm-e  milk  of  lime 
is  next  added  in  slight  excess,  the  mixture  boiled,  and  the  precipi- 
tate (mainly  magnesium  hydrate)  filtered,  and  washed  with  hot 
water  until  it  no  longer  shows  a  lithium  reaction.  The  filtrate  is 
precipitated  with  ammonium  oxalate,  and  the  precipitate  washed, 
ignited,  dissolved,  evaporated,  and  tested  for  lithium.  If  a  reaction 
be  still  obtained,  the  solution  is  again  precipitated  and  filtered. 
The  filtrate  or  filtrates  are  evaporated  to  dryness,  the  ammonia 
salts  expelled  ;  the  residue  moistened  with  hydrochloric  acid  ;  water 
added  ;  the  solution  evaporated  to  dryness  on  a  water  bath,  and  the 
treatment  with  milk  of  lime,  etc.,  repeated,  using  small  quantities 
of  the  reagents,  and  constantly  testing  the  separated  precipitates 
for  lithium.  Having  expelled  the  ammonia  salts  a  second  time, 
moistened  with  hydrochloric  acid  and  evapoi-ated,  the  lithium  is 
separated  as  lithium  phosj^hate,  according  to  the  method  mentioned 
in  Zeifschr.  anahjf.  Ghevi.,  i.,  42.  The  precipitate  is  then  dissolved 
in  hydrochloric  acid,  and  tested  to  find  out  whether  the  dilute 
solution  gives  with  excess  of  ammonia  a  small  precipitate  in  the 
cold.  If  such  be  the  case,  it  is  redissolved  in  hydrochloric  acid, 
precipitated  with  ammonia,  filtered,  weighed,  and  deducted  from 
the  lithium  phosphate  obtained.  The  filtrate  from  the  phosphate  is 
tested  for  caesium  and  rubidium. 

(5)  The  residue  insoluble  in  water  is  treated  with  water  in  a  largo 
porcelain  dish,  and  hydrochloric  acid  (with  five  drops  of  sulphuric 
acid)  added.  Solids  adhering  to  the  copper  still  are  removed  by 
treatment  with  acetic  acid,  and  the  Avhole  is  evaporated  to  dryness. 
The  residue  is  treated  with  hydrochloric  acid  and  water  ;  the  silicic 
acid,  etc.,  filtered  off;  the  precipitate  boiled  with  sodium  carbonate 
until  the  silicic  acid  is  dissolved  ;  the  solution  filtered,  and  the 
residue  washed,  incinerated  and  fused  with  sodium  carbonate, 

The  fused  mass  is  boiled  with  water,  filtered,  washed,  and  dis- 
solved in  dilute  hydrochloric  acid  ;  the  solution  is  evaporated,  and 
the  residue  is  taken  up  with  water  and  a  few  drops  of  hydrochloric 
acid.  The  solution  is  then  pi'ecipitated  with  a  few  drops  of  dilute 
sulphuric  acid,  left  to  settle,  filtered,  and  the  filtrate  is  treated  with 
three  volumes  of  alcohol.  If  a  precipitate  is  formed,  it  is  strontium 
sulphate  or  calcium  sulphate.  The  filtered  barium  sulphate  is,  after 
washing,  brought  into  a  funnel  closed  at  the  bottom  by  a  tap,  and 


PHARMACEUTICAL    CHEMISTRY.  87 

treated  with  a  concentrated  solution  of  ammonium  carbonate.    After 
twelve  hours  the  tap  is  opened,  the  liquid  run  out  very  slowly,  the 
precipitate  washed  and  treated  with  very  dilute  nitric  acid,  to  re- 
move any  strontium  mixed  therewith;  then  washed  with  water, 
dried,  ignited,  and  weighed  as  pure  barium  sulphate.     The  filtrate 
from  the  silicic  acid  is  diluted  with  water,  treated  while  warm  with 
sulphuretted  hydrogen,  to  remove  traces  of  tin  gone  over  into  the 
solution ;  the  filtrate  is  then  boiled  with  nitric  acid,  the  precipitate 
dissolved  in  hydrochloric  acid,  the  ferric  oxide  separated  by  pre- 
cipitation as  basic  salt,  and  the  filtrate  supersaturated  with  ammo- 
nia.     In  the  solution,  filtered,  if  necessary,  the  manganese  is  pre- 
cipitated  with   ammonium  sulphide,  and  the  lime   in   the  filtrate 
precipitated  with  ammonia  and  carbonate  of  ammonia.    The  filtered 
and  washed    precipitate   is    dissolved   in  nitric  acid   (adding    the 
above-mentioned  nitric   acid   solution   containing    strontium),  and 
evaporated  in  a  retort  on  a  sand  bath,  exhausting  the  moisture  by 
means  of  an  air  pump.     The  residue  is  then  treated  with  not  too 
large  a  quantity  of  ether  and  alcohol,  so  as  to  dissolve  the  nitrate 
of   calcium.      The  residue  is  dissolved  in  water,  evaporated  to  a 
small  bulk,  and  a  concentrated  solution  of  ammonium  sulphate  (1 
in  4)  added  in  excess.     After  twelve  hours  the  solution  is  filtered 
through  a  small  filter  (the  above-mentioned  strontium  precipitate  ob- 
tained by  the  treatment  with  alcohol  is  added  to  the  same),  and  after 
washing  with  ammonium  sulphate,  dried  and  ignited  as  sulphate. 

7.  Determination  of  the  PJwspJioric  Acid. — The  phosphoric  acid 
might  be  estimated  in  the  determination  of  the  ferric  oxide,  alu- 
mina, etc.,  in  Nos.  2  and  6.  It  is  best,  however,  to  determine  it  in  a 
separate  portion  of  the  water.  About  6  litres  are  evaporated  with 
hydrochloi'ic  acid,  the  silicic  acid  is  separated,  the  filtrate  evapo- 
rated with  nitric  acid  to  dryness,  the  residue  dissolved  in  nitric 
acid  and  water,  precipitated  with  a  nitric  acid  solution  of  ammo- 
nium molybdate,  and  the  phosphoric  acid  determined  as  pyrophos- 
phate of  magnesia. 

8.  Determination  of  the  Nitric  Acid  and  Ammonia. — If  nitric  acid 
and  ammonia  are  present  in  determinable  quantities,  the  method 
mentioned  in  Anl.  zur  qtiant.  Anal,  5  Aufl.,  pp.  696,  697,  is  used. 
If  the  water  contains  large  quantities  of  organic  substances,  it 
is  better  to  replace  the  soda  ley  necessary  to  expel  the  ammonia  by 
magnesia. 

Butter  Analysis.  Dr.  J.  Muter.  (Abstracted  from  the  J-ucJt/s^, 
1876,  No.  1.)  The  process  adopted  by  the  author  for  the  full  analy- 
sis of  butter  is  as  follows  : — 


88  YEAR-BOOK    OF    PHARMACY. 

1.  1500  grains  of  the  butler  are  placed  in  a  couutcvpoised 
porcelain  dish  over  a  very  low  gas  flame,  and  stirred  witli  a  ther- 
mometer at  a  heat  not  exceeding  230°  F.,  until  all  the  water  is  given 
off,  which  is  indicated  by  effervescence  entirely  ceasing,  and  the 
curd  and  salt  settling  perfectly  down  to  the  bottom  of  the  dish, 
leaving  the  absolutely  clear  melted  fat.  Tlie  whole  is  then  cooled 
and  weighed,  and  the  loss  calculated  to  percentage  of  icater.  This 
is  the  only  method  of  absolutely  and  rapidly  drying  a  fat,  and  the 
large  quantity  taken  ensures  a  more  perfect  estimate  of  the  true 
amount  of  water  in  the  sample.  The  temperature  of  230°  has  not 
the  slightest  influence  on  butter  fat. 

2.  The  fat  is  melted  at  a  gentle  heat  and  poured  off"  as  far  as 
possible  into  a  beaker,  without  disturbing  the  sediment.  The  re- 
mainder is  poured  on  a  weighed  filter,  placed  over  a  beaker  in  the 
drying  chamber,  and  when  drained  the  basin  and  filter  are  rinsed 
with  petroleum  spirit,  to  remove  all  the  traces  of  fat ;  and  the  filter 
being  dried  and  weighed  gives  cwd  plus  ash. 

3.  The  filter  after  being  weighed  is  placed  in  a  weighed  platinum 
crucible  and  gently  ignited.  This  gives  ash  called  salt  in  the 
report. 

4.  The  fat  poured  off"  from  Xo.  2 — which  will  generally  be  about 
1200  grains — if  absolutely  clear,  is  at  once  used  for  physical  and 
chemical  examin-ation ;  but  if  not  perfectly  free  from  specks,  it  must 
be  filtered  through  a  Swedish  filter  kept  hot  on  the  water  bath.  The 
processes  necessary  are  the  taking  the  specific  gravity  of  the  fat  at 
100  F.,  and  if  that  gives  an  adverse  indication,  the  estimation  of 
the  total  fatty  acids  of  the  butter  fat,  both  soluble  and  insoluble. 

Determination  of  the  Specific  Gravity. — A  1000  grain  bottle  is  pro- 
cured with  rather  a  pear-shaped  neck,  and  fitted  with  a  thermometer 
stopper  ranging  from  32°  to  140°  F.  The  long  mercurial  bulb 
comes  exactly  down  the  centre  of  the  bottle,  and  the  scale  is  up 
above  the  stopper.  The  bottle  is  placed  on  the  balance,  and  an 
accurate  counterpoise  prepared  for  it.  It  is  then  filled  with 
recently  boiled  distilled  water,  at  95°  F.  The  stopper  is  inserted 
and  the  whole  at  once  plunged  up  to  the  neck  into  fi  12  oz.  squat 
beaker  partially  filled  with  distilled  water  at  103°  F.,  in  which  is 
placed  a  thermometer.  As  the  temperature  rises  in  the  bottle,  the 
water  leaks  out  at  the  stopper,  and  in  a  few  minutes  (if  the  quantity 
of  water  in  the  beaker  be  properly  regulated)  a  time  arrives  when 
the  temperature  of  both  thermometers  equalize  themselves  at  100°. 
The  point  between  the  stopper  and  the  bottle  is  instantly  wiped 
with  a  small  piece   of   filter  paper,  to  absorb  loose  water ;  and  the 


i 


PHAEMACEUTICAL    CHEMISTRY.  89 

bottle  is  lifted  oiit,  tboronghly  cleansed,  and  weigtied.  By  repeating 
this  three  times  the  actual  contents  of  the  bottle  at  100°  F.  is  ob- 
tained, and  the  weight  taken  before  a  fall  of  more  than  5°  takes 
place.  This  weight  of  water  is  scratched  on  the  bottle  with  a 
diamond,  and  all  is  ready  for  the  butter.  The  pure  butter  fat, 
pi-epared  as  already  described,  is  taken  from  the  bath  and  cooled  to 
95°  F. ;  it  is  then  poured  into  the  bottle,  and  the  whole  operation 
repeated  thrice,  exactly  as  with  the  water,  and  the  mean  of  the 
three  weighings  thus  obtained  is  divided  by  that  of  the  water.  The 
contrivance  of  having  a  " r/^^t'^f;' "  fat  heated  by  '''falling''''  water 
until  the  two  equalize,  is  the  height  of  accuracy,  and  moreover  gives 
an  appreciable  rest  in  the  variation  of  the  temperature  sufficient  to 
enable  the  excess  of  fat  which  has  leaked  out  to  be  removed  exactly 
at  the  required  temperature. 

In  the  author's  opinion,  any  butter  showing  a  specific  gravity 
of  over  'Oil  may  be  safely  passed  over  without  analysis,  as  being 
good. 

The  Total  Fatty  Acids. — About  10  grams  (or  150  grains)  of  [the 
butter  fat  at  100°  F.  are  weighed  by  difference  from  a  suspended 
tube  into  a  clean,  dry,  15  ounce  flask,  and  5  grains  of  potassium  hy- 
drate, with  two  fluid  ounces  of  rectified  spirit,  are  added.  The  flask 
is  placed  in  a  basin  with  hot  water,  and  kept  boiling  for  a  consider- 
able time,  until  on  adding  water  not  the  faintest  turbidity  occurs. 
Ten  ounces  of  water  are  added,  and  evaporation  continued  (just 
short  of  boiling)  until  all  traces  of  alcohol  ai-e  dissipated.  The 
contents  of  the  flask  are  then  made  up  to  7  ounces  with  nearly 
boiling  water;  and  a  good  fitting  cork  having  been  introduced, 
through  which  just  passes  a  tube  2  feet  long  and  ending  in  a  small 
funnel,  5  grams  of  full  strength  sulphuric  acid  are  poured  in  down 
the  tube,  followed  by  some  water.  The  whole  is  then  agitated  with 
a  circular  motion  until  the  soap,  which  rises  suddenly,  is  changed  into 
a  perfectly  clear  and  transparent  stratum  of  fatty  acids.  The  flask 
and  contents  are  then  cooled  down  to  40°  F.,  till  a  perfectly  solid 
cake  of  fatty  acid  forms.  A  few  drops  of  cold  water  are  run  in  to 
wash  the  tube,  and  the  cork  having  been  removed,  a  small  jiiece  of 
fine  cambric  is  placed  over  the  mouth  of  the  flask,  held  i)i  situ  by 
an  ordinary  indiarubber  ring.  The  fat  cake  is  caused  to  detach 
itself  from  the  sides  of  the  flask  by  a  gentle  movement,  and  then 
the  filtrate  is  decanted,  without  breaking  the  cake,  into  a  litre  test 
mixer  with  a  good  stopper.  About  an  ounce  of  cold  water  is 
poured  into  the  flask  through  the  cambric,  and  the  whole  cake  and 
flask  rinsed  out  by  gently  turning  round,  and  the  washings  added  to 


90 


YEAR-BOOK    OF    PHARMACY. 


the  filtrate.  Six  ounces  of  water  at  120°  are  now  added  through  the 
muslin,  which  is  then  quickly  detached,  and  tlie  cork  and  tube  in- 
serted. The  whole  is  again  heated,  this  time  to  200^  and  kept 
constantly  agitated  with  a  circular  but  not  a  jerky  motion  for  five 
minutes.  This  agitation  so  divides  the  fat  that  it  almost  forms  an 
emulsion  with  the  water,  and  is  the  only  means  of  thoroughly  and 
rapidly  washing  fatty  acids  without  loss.  In  practice  no  butyric 
acid  comes  off  at  200°;  but  any  trace  that  might  do  so  is  caught  in 
the  long  tube.  The  cooling  and  filtering  are  then  again  proceeded 
with  as  above  described  (the  filtrate  being  added  to  the  contents  of 
the  test  mixer),  and  tlie  washings  are  repeated  alternately  cold 
with  1  ounce,  and  hot  with  6  ounces  of  water,  until  they  do  not  give 
the  slightest  change  to  neutral  litmus.  After  thoroughly  draining 
the  residual  cake  by  letting  the  flask  stand  upside  down  for  some 
time,  the  cambric  is  removed  and  the  flask  is  laid  out  on  its  side  in 
the  drying  oven  with  a  support  under  the  neck,  until  the  acids  are 
thoroughly  fused,  when  they  are  poured  while  hot  into  a  tared 
platinum  capsule,  dried,  and  weighed.  The  film  of  fatty  acid  still 
remaining  on  the  flask  is  rinsed  out  with  ether,  and  dried  in  a  small 
weighed  beakei',  and  the  weight  added  to  the  whole.  If  any  drops 
of  water  be  observed  under  the  fatty  acids  in  the  capsule  after  an 
hour's  drying,  the  addition  of  a  few  drops  of  absolute  alcohol  will 
quickly  cause  them  to  dry  off.  If  any  trace  of  fat  is  on  the  cambric, 
it  should  be  also  dried  and  extracted  with  ether ;  but  with  care  not 
to  break  the  cake  at  the  last  pouring  off  this  does  not  occur. 

The  process  is  absolutely  accurate,  and  the  merest  tyro  cannot 
make  any  loss  so  long  as  he  does  not  deliberately  shake  the  melted 
acids  against  the  cork,  which  he  could  not  do  if  he  practises  a  circu- 
lar agitation  while  washing.  The  filtrate  in  the  test  mixer  is  now 
made  to  an  absolute  bulk,  and  in  200  c.c.  the  total  acidity  is  taken 
with  a  weak  solution  of  sodium  hydrate.  The  solution  generally 
used  represents  "01  of  NH3  in  each  c.c,  as  it  serves  also  for  nitrogen 
combustions ;  but  a  iiscful  strength  would  be  decinormal  soda,  con- 
taining "004  Na  H  0  in  each  c.c.  The  acidity  found  is  multiplied  by 
five,  calculated  to  H2  S  O4,  and  noted  as  "  total  acidity  as  H,,  S  O4." 
100  c.c.  are  next  taken  and  precipitated  with  barium  chloride  in  the 
presence  of  a  strong  acidulation  with  hydrochloric  acid,  well  boiled, 
and  washed  by  three  decantations,  boiling  each  time  ;  and,  lastly, 
on  a  filter,  till  every  trace  of  soluble  barium  is  removed.  The  pre- 
cipitate is  dried,  ignited,  and  weighed  as  usual,  multiplied  by  ten, 
and  calculated  to  Ho  S  O4,  and  noted  as  "  total  sulphuric  acid." 
La.stly,  100  c.c.  are  evaporated  to  dryness  over  the  water  bath  in  a 


PHAiniACEUTICAL    CHEMISTRY.  91 

tared  platinum  dish  holding  120  c.c,  and  furnished  with  a  cover  of 
platinum  foil,  also  tared.  When  dry  the  dish  is  covered  and  heated 
over  a  bunsen  till  all  fumes  cease  ;  and  a  fragment  of  pure  ammo- 
nium carbonate  having  been  added,  the  whole  is  again  ignited  and 
weighed.  The  amount  of  potassium  sulphate  found  is  multiplied  by 
10  and  calculated  to  Ho  S  O4,  and  noted  as  "combined  sulphuric 
acid."  The  rest  of  the  calculation  is  obvious  from  the  following 
example : — 

Ten  grams  talicn. 

Total  acidity  as  Hj  S  0^ 0-814 

Total  H;  S  O4 4-9 

Combined  H.  S  O4 4-1 

4.9_4-4=--5freeH2S04 

0-814— -5  =  -314  acidity  due  to  butter  acids  stated  as  H.  S  O4 

Then  '^^^^   '^°  =  -504  butyric  acid   in  10  grams   taken,  wliich 
equals  5-64  per  cent. 

The  author  regards  88  per  cent,  of  insoluble  fatty  acid  as  a  fair 
standard  of  butter  calculation,  if  associated  with  at  least  6'3  of  solu- 
ble acids.  But  he  would  not  apply  any  charge  of  admixture  to  a 
butter  which  showed  less  than  89"5  insoluble  with  5  of  soluble  acids. 

Butter  Analysis.  A.  Dupre.  (From  a  paper  read  before  the 
Society  of  Public  Analysts,  June  14th,  1876.)  On  the  strength  of 
numerous  experiments,  the  author  has  adopted  the  following  me- 
thod, which  in  his  opinion  leaves  nothing  to  be  desired  on  the  score 
either  of  facility  of  execution  or  of  accuracy  : — About  o  grams  of 
the  dry  filtered  butter  fat  are  weighed  into  a  small  strong  flask  ;  25 
c.c.  of  a  normal  alcoholic  soda  solution  are  added  ;  the  flask  is  closed 
by  means  of  a  well-fitting  caoutchouc  stoppei',  firmly  secui'ed  by  a 
piece  of  canvas  and  string,  and  heated  in  a  water  bath  for  about  one 
hour.  When  cool  the  flask  is  opened,  the  contents — which  are 
semi-solid — carefully  liquefied  by  heat  and  washed  into  a  flask  with 
hot  water.  This  flask  is  now  heated  for  some  time  on  a  water  bath 
to  expel  the  alcohol,  some  more  hot  water  is  added,  and  25  c.c. 
of  diluted  sulphuric  acid,  somewhat  stronger  than  the  alkali  used, 
are  run  in.  The  contents  are  allowed  to  cool,  and  the  acid  aqueous 
solution  below  the  cake  of  fatty  acids  is  passed  through  a  filter. 
The  fatty  acids  in  the  flask  are  washed  by  hot  water  in  the  manner 
recommended  by  Dr.  Muter,  i.e.,  each  time  allowed  to  cool ;  all 
the  washings  are  passed  through  a  filter.  The  author  uses  no  cam- 
bric, but  passes  everything  through  paper.  With  care  scarcely 
any  of  the  fatty  acid  will  find  its  way  into  the  filter.     After  the 


92  YEAR-BOOK   OP    PHARMACY. 

■washing  with  water  is  completed  and  the  flask  drained,  lie  Avaslies 
any  fatty  acid  that  may  be  on  the  filter  into  the  flask  hy  means  of 
a  mixture  of  alcohol  and  ether  on  a  water  bath,  and  finally  dries 
the  fatty  acids  in  the  flask  at  a  temperature  of  105°  C.  The  drying 
can  be  done  readily  if  the  melted  fat  is  now  and  then  shaken  briskly, 
so  as  to  sub-divide  the  water  as  much  as  possible.  In  this  way  the 
acids,  when  once  in  the  flask,  are  not  taken  out  until  their  weight 
has  been  taken,  thus  reducing  the  risk  of  loss  to  a  minimum. 
Meanwhile  the  acidity  of  the  aqueous  filtrate  and  washings  is  esti- 
mated by  decinormal  soda  solution.  Subtracting  from  the  amount 
required  the  proportion  necessaiy  to  neutralize  the  excess  of  acid 
added  in  decomposing  the  soap,  the  rest  represents  the  soluble  fatty 
acids  contained  in  the  butter  taken,  and  on  the  assumption  of  its 
being  butyric  acid  we  can,  of  course,  calculate  the  amount  of  this 
acid  present.  When  once  the  equivalent  of  the  soluble  acids  -pve- 
sent  in  butter  is  fairly  determined,  this,  of  course,  will  have  to  be 
substituted  for  that  of  butyric  acid.  The  results  thus  obtained  are 
very  accurate,  and  the  process  is  very  simple  in  execution.  The 
author  has  satisfied  himself  by  repeated  experiments  that  the  alka- 
linity of  the  alcoholic  soda  solution  by  itself  is  not  altered  by  the 
process. 

The  author  places  no  reliance  on  the  specific  gravity  test,  as  he 
finds  that  mutton  dripping,  and  other  fats  likely  to  be  used  as 
adulterants  of  butter,  may  acquire  a  sp.  gr.  above  "911  by  being 
strongly  and  repeatedly  heated.  He  thinks,  however,  that  any 
sample  of  butter  showing  a  sp.  gr.  below  "Qll  may  safely  be  pro- 
nounced adulterated. 

In  a  subsequent  note.  Dr.  Dupre  states  that  he  has  effected  the 
saponification,  decomposition  of  the  soap,  and  the  washing  and 
drying  of  the  fatty  acids  at  ordinary  temperature,  thus  still  further 
reducing  the  risk  of  breaking  up  the  higher  into  lower  acids.  The 
saponification  is  i-eadily  effected  by  using  a  sufliciency  of  alcoholic 
soda.  Between  four  and  five  grams  of  the  dry  butter  fat  were 
shaken  up  for  several  minutes  with  100  c.c.  of  normal  alco- 
holic soda.  The  batter  soon  dissolves,  but  after  a  time  the  solution 
gelatinises  to  a  clear,  transparent  jelly.  (The  temperature  of  the 
laboratory  at  the  time  of  these  experiments  ranged  between  22°  and 
50°).  This  jelly  is  now  allowed  to  stand  over  night,  during  Avhich 
time  the  smell  of  butyric  ether,  very  strong  at  first,  entirely  dis- 
appears. In  one  of  the  experiments  the  alcohol  was  allowed  to 
evaporate  spontaneously,  before  the  acid  was  added  ;  in  the  other 
(made  with  a  different  sample  of  butter),  the  soap  was  dissolved  in 


PHARMACEUTICAL    CHEMISTRY.  93 

about  a  half-litre  of  -water,  and  at  once  decomposed  by  the  addition 
of  liydrochloric  acid.  The  fatty  acids,  which  separated  in  white 
curdy  masses,  were  thoroughly  washed  on  a  jfilter  with  cold  water, 
about  four  litres,  dried  in  vacuo  over  oil  of  vitriol,  and  weighed. 
The  results  of  experiment  show  that  butter  fat  yields  the  same  pro- 
portion of  insoluble  fatty  acids,  whether  saponified  with  or  without 
the  aid  of  heat. 

The  Preparation  of  Nicotine.  W.  Kirch  man  n.  (Archiv  der 
Plmrm.  September,  1876,  209.)  The  author  proposes  the  follow- 
ing simple  method  of  preparing  pure  nicotine.  A  tin  vessel, 
provided  with  two  tubulurcs,  is  filled  with  tobacco,  which  is 
previously  damped  with  sodium  carbonate.  One  of  the  tubu- 
lures  admits  a  glass  tube  reaching  nearly  to  the  bottom  of  the 
vessel ;  the  other  is  provided  with  a  glass  tube  merely  jDcne- 
trating  the  cork.  The  vessel  lis  made  air-tight,  placed  into  a 
boiling  hot  steam  bath,  and  a  rapid  stream  of  carbonic  acid 
gas  passed  through  it,  entering  the  vessel  by  the  longer,  and 
leaving  it  by  the  shorter  tube ;  the  latter  dips  into  a  mixture  of 
alcohol  and  dilute  sulphuric  acid.  In  this  manner  a  large  yield 
of  perfectly  colourless  nicotine  sulphate  is  obtained.  In  order  to 
obtain  the  pure  alkaloid,  caustic  baryta  is  added  to  the  solution, 
the  latter  evaporated  to  dryness,  and  ihe  pure  nicotine  extracted 
with  ether. 

A  portion  of  highly  concentrated  solution  of  acid  nicotine  sulphate 
(bisulphate),  saturated  with  alumina  hydrate,  deposited  in  a  short 
time  handsome  octahedric  crystals,  which  the  author  considers  to 
be  nothing  else  but  nicotina  alum,  although  he  adds  that  he  is  not 
aware  of  a  previously-known  case  where  a  tertiary  diamine  base 
could  take  the  place  of  ammonia  in  alum. 

The  same  process  could  probably  be  employed  for  the  preparation 
of  conia  (from  Gonium  macidatnm,  L.  ;  hemlock)  and  sparteina 
(from  Spartium  scoimrium,  L.  =  Cijtisus  scoparms,  Link.,  Sarotham- 
niis  scoparius,  Wimmer  ;  bi'oom.) 

The  Essential  OilofCubehs.  A.  Oglialoro.  (Journ.  Chem.  Soc, 
from  Gazetta  Chim.  Ital.,  v.,  467.)  Whilst  examining  a  specimen 
of  essence  of  cubebs,  the  author  found  that  he  obtained  a  hydro- 
carbon, Cin  Hjg,  boiHng  at  160°,  which  appears  to  have  been  un- 
noticed by  any  previous  experimenter,  although  he  did  not  succeed 
in  separating  the  hydrocarbon  of  boiling  point  230°,  mentioned  by 
Schmidt.  This  induced  him  to  prepare  some  of  the  essential  oil 
from  cubebs  by  distilling  the  substance  in  a  current  of  steam  in  a 
copper  still ;  the  yield  was  about  four  per  cent.,  and  the  product. 


94  TEAR-BOOK    OF    PHARMACY. 

when  submitted  to  careful  rectification  after  being  dried  over  cal- 
cium chloride,  yielded  a   small  quantity  of  a  hydrocarbon,  Cjo  Hjg, 
belonging  to  the  terpene  series,  boiling  at  lo8°-16o°,  and  a  con- 
siderable portion  boiling  at  250^-270°, — evidently  a  mixture, — but 
no  trace  of  the  hydrocarbon  boiling  at  230°,  observed  by  Schmidt. 
The  portion  boiling  at  250°-2r0°  was  mixed  with  half  its  weight 
of  ether   and  saturated  with  hydrochloric  acid ;    by  this   means  a 
crystalline  hydrochloride,  of  the  composition  Ci,-,  H24  H  CI,  was  sepa- 
rated ;    whilst   the   mother-liquor,  after   evaporation   of    the   ether 
and  separation  of  a  further   portion  of  the  hydrochloride  which 
crystallized   out,  was  washed   with  dilute  alkali,  dried,  and  sub- 
mitted to  fractional  distillation.     The   greater  portion  passed  over 
at  262°-2G3°,  and   possessed  a  slight  IsBvoi-otatory  power,  although 
it  is  doubtful  whether  this  is   inherent  in   thef  hydrocarbon,  or  is 
due  to  the  admixture  of  a  small  amount  of  that  which   forms  the 
crystalline    hydrochloride.       The    hydrochloride    crystallizes    from 
boiling  alcohol  in  long  colourless  needles,  which  melt  at  117°-118°; 
and  when  heated  for  some  time  to  170°-180°  with  water  in  sealed 
tubes,    is    completely   decomposed    into   hydrochloric   acid    and   a 
hydrocarbon   of  the  formula  C15  H04.       This,  after  purification  by 
rectification  from  sodium,  has  a  density  of  0"9289  at  0°,  and  boils 
at  264°-2Go°.     It  deflects  the  polarized  ray  to  the  left.     The  hydro- 
chloride also  has  considerable  action  on  polarized  light. 

The  Fluorescent  Matter  in  Atropa  Belladonna.  R.  Fassbendeo. 
(Zeifschr.  dcsoexterr.  Apoth.  Ft'/-.,  xi.,'50C  ;  Fhann.  Zeit.  [3],  vii.,  506.) 
The  author  publishes  some  further  information  respecting  the  blue 
fluorescent  matter  discovered  by  Richter.  It  is  found  in  all 
parts  of  Atro2]a  belladonna,  and  is  distinguished  by  its  great  per- 
manence and  very  strong  fluorescence,  which  can  be  recognised 
even  when  extremely  diluted.  The  author  found  it  in  all  the 
commercial  extracts  of  belladonna  he"!  examined ;  whether  com- 
mercial specimens  of  atropa  and  it  salts  are  free  from  this  sub- 
stance, he  is  not  in  a  position  to  state. 

In  order  to  show  how  extremely  small  a  quantity  of  this  substance 
can  be  distinctly  recognised,  the  author  crushed  two  unripe  belladonna 
berries  in  some  water,  evaporated  the  liquor  in  a  water  bath,  treated 
the  residue  with  alcohol,  filtered,  evaporated  the  solution,  and  again 
dissolved  the  residue  in  water.  The  filtered  solution,  which  percept- 
ibly reddened  blue  litmus  paper,  was  digested  with  animal  black, 
which  absorbed  the  colouring  matter  ;  the  charcoal  was  treated  with 
alcohol  at  a  gentle  heat,  a  few  drops  of  ammonia  added,  the  liquor 
filtered,  and  the  charcoal  again  Avashed  with  alcohol.     The  filtrate 


PHAKMACEUTICAL    CHEMISTRY.  95 

■was  clearly  fluorescent,  and  when  diluted  with  200  c.c.  of  alcohol, 
the  characteristic  blue  colour  was  still  distinctly  perceptible  if  looked 
at  from,  above.  The  great  permanence  of  this  substance  may  be 
shown  with  a  few  drops  of  a  less  dilute  solution  mixed  with  a  drop 
of  ammonia  on  a  watch  glass ;  after  the  rapid  drying  up  of  this 
liquid  upon  a  warm  day,  the  reaction  is  reproduced  by  the  addition 
of  more  ammonia.  Besides  the  colouring  matter,  there  is  obtained 
by  the  above  method  of  preparation  a  yellow  resinous  body,  insoluble 
in  water  and  very  soluble  in  alcohol. 

A  New  Reagent  for  Glucose.  A.  Soldaini.  {Ber.  der  deutsch. 
Chem.-Ges.,  ix.,  1126.)  The  author  recommends  a  solution  of 
potassio-cai-bonate  of  copper  as  a  test  for  glucose.  The  reagent  is 
prepared  by  dissolving  15  grams  of  precipitated  carbonate  of  copper 
gradually,  with  the  aid  of  heat,  in  a  solution  of  410  grams  of  bicar- 
bonate of  potassium  in  1400  c.c.  of  water.  It  keeps  well  and  under- 
goes no  change,  even  on  prolonged  boiling.  It  is  reduced  by  glucose 
and  sugar  of  milk,  but  not  by  pure  cane  sugar,  dextrin,  or  starch. 
Tartaric  acid,  uric  acid,  and  normal  urine  do  not  affect  it ;  but 
tannic  and  formic  acid,  when  heated  with  it,  effect  a  separation  of 
cuprous  oxide. 

OccuiTence  of  Glucose  in  Spirit  of  Wine.  G-.  Salomon. 
(Chem.  Gentralhl.,  No.  33.)  Commercial  alcohol  has  been  observed 
to  leave  on  evaporation  a  residue  which  reduces  Fehling's  solution. 
In  one  instance  the  author  obtained  from  one  litre  of  spirit  0"13 
gi-am  of  glucose,  emanating  probably  from  liquors  previously  kept 
in  the  same  cask.  A  knowledge  of  the  occurrence  of  this  impurity 
may  be  important  in  analytical  investigations. 

Taxine,  a  Poisonous  Alkaloid  contained  in  the  Leaves  and  Seeds 
of  Taxus  Baccata.  W.  Mavine.  (Chem.  Centrcdhl.,  1876,  166 ; 
Journ.  ClieJii.  Soc,  April,  1877.)  Although  cases  of  poisoning  by 
yew  berries  have  been  confirmed  in  former  times,  and  also  recently, 
the  poisonous  effects  of  the  fruit  and  seeds  of  the  yew  tree  are  dis- 
puted from  many  sides,  while  the  strongly  toxic  action  of  the  other 
portions  of  the  tree  are  known  generally. 

Lucas  isolated  from  the  leaves  of  this  tree  three  grains  of  a  body 
which  he  called  taxine,  and  gave  a  few  reactions  regarding  it.  For 
its  preparation  Stass's  method  for  detecting  alkaloids  was  followed 
out,  without  giving  satisfactory  results.  The  following  process  was 
more  successful : — The  leaves  or  seeds  are  powdered,  and  repeatedly 
exhausted  with  ether ;  the  extracts  are  mixed,  and  the  ether  is  dis- 
tilled off.  The  residue,  which  when  obtained  from  the  leaves  forms 
a  green  resinous  mass,  having  a  peculiar  aromatic  smell  and  sharp 


96  YEAR-BOOK    OF    PHARMACY. 

taste,  while  that  fi-om  the  seeds  is  a  large  quantity  of  a  fatty  oil, 
"was  repeatedly  shaken  up  with  water,  acidulated,  and  slightly 
warmed.  The  water  separated  from  the  residue  was  filtered,  and  in 
the  clear  and  colourless  filtrate  the  taxine  Avas  precipitated  by  am- 
monia or  fixed  alkali,  in  snow-white  bulky  flakes.  When  washed 
and  dried  over  sulphuric  acid,  it  forms  a  white  crystalline  powder, 
which  is  scarcely  soluble  in  distilled  water,  readily  soluble  in  acidu- 
lated water,  alcohol,  ether,  chloroform,  beuzin,  and  carbon  disul- 
phide  ;  and  insoluble  in  petroleum  ether.  In  has  no  smell,  but  a 
very  bitter  taste.  Pure,  concentrated  sulphuric  acid  reddens  it ; 
nitric,  hydrochloric,  and  phosphoric  acids  dissolve  it  without  change 
of  colour.  With  most  of  the  reagents  characteristic  of  alkaloids — 
tannic  acid,  phosphomolybdic  acid,  potassio-mercuric  iodide,  po- 
tassio-cadmic  iodide,  potassio-bismuthic  iodide,  iodo-potassio  iodide, 
potassio-argentic  cyanide,  potassic  bichromate,  picric  acid  —  it 
yields,  in  an  acid  solution,  amorphous  precipitates.  Platinic 
chloride,  auric  chloride,  mercuric  chloride,  potassio-platinous 
cyanide  are  not  precipitated.  It  does  not  form  crystallized  salts 
with  the  ordinary  acids.  It  is  nitrogenous  (evolves  ammonia  when 
heated  with  freshly  ignited  soda-lime),  melts  at  80°,  and  burns  with- 
out residue  when  heated  more  strongly.  Taxine  is  present  in  the 
leaves  in  larger  quantities  than  in  the  seeds  of  the  yew  tree. 

The  Dissociation  of  the  Vapour  of  Calomel.  H.  Debray. 
{Comptes  Reiulus,  Ixxxiii.,  330.)  Odling  and  Erlenmeyer  regard  the 
dissociation  of  the  vapour  of  calomel  at  440°  C.  as  complete,  and 
base  their  opinion  on  the  density  of  the  vapour  and  the  observation 
that  a  strip  of  gold  placed  in  the  vapour  becomes  amalgamated  and 
also  coated  with  an  incrustation  of  mercuric  chloride.  This  view, 
however,  is  not  borne  out  by  the  author's  experiments.  If  it  be 
assumed  that  the  vapour  at  the  tem]3erature  named  represents  a 
mixture  of  equal  volumes  of  the  vapour  of  mercury  and  mercui^ic 
chloride,  the  tension  of  the  vapour  of  mercury  in  this  mixture 
would  amount  to  half  an  atmos})hcre ;  and  unless  the  tension  of  dis- 
sociation of  gold  amalgam  is  proved  to  be  less  than  half  an  atmos- 
phere, the  author  declines  to  regard  the  experiment  with  the  strip 
of  gold  as  conclusive.  If  it  be  more  than  half  an  atmosphere,  the 
gold  could  not  amalgamate  in  such  a  mixture.  His  own  experi- 
ments show  that  a  strip  of  gold  heated  to  440°  is  not  amalgamated 
in  the  vapour  of  mercury  at  the  ordinary  atmospheric  pressure;  and 
that  on  heating  calomel  to  the  same  temperature,  and  placing  a 
curved  gilt  silver  tube,  through  which  cold  water  is  kept  running, 
into  the  vapour  for  a  few  seconds,  the  tube  becomes  coated  with 


\ 


PHARMACEUTICAL    CHEMISTRY.  97 

calomel  intermixed  with  a  small  quantity  of  metallic  mercury.  He 
therefore  arrives  at  the  conclusion,  that  though  some  decomposition 
takes  place,  the  dissociation  at  440^  is  not  complete. 

Ostruthin.  E.  von  Grorup-Besanez.  (Llebif/s  Ann.  d.  Gliem., 
clxxxiii.,  321-343;  Amer.  Journ.  of  Pharm.,  May,  1877.)  This 
body  was  discovered  by  the  author  in  1874,  in  the  root  of  Im- 
peratoria  ostruthium.  The  following  is  an  outline  of  the  process 
by  which  the  largest  yield  has  been  obtained  : — 

The  young  roots  of  masterwort,  one  to  two  years  old,  are  cut  and 
digested  with  90  per  cent,  alcohol  at  50°  to  60°  C,  until  the  liquid 
ceases  to  become  coloured  ;  the  mixed  tinctures  are  distilled  to  one- 
third,  and  this  then  evaporated  until  on  cooling  a  thick  liquid  re- 
mains. This  residue  is  exhausted  by  a  mixture  of  three  parts  of 
ether  and  one  of  ligroin  of  low  boiling  point,  until  a  firm  plaster- 
like mass  remains.  The  solution  is  mixed  with  more  ligroin,  which 
separates  a  brown  sticky  mass,  and  the  decanted  liquor  is  evaporated 
spontaneously  from  flat  dishes,  and  if  necessary  decanted  from  the 
oily  sediment  forming.  Yellow  crystals  are  afterwards  deposited, 
which  are  freed  from  adhering  resinous  matter  by  spreading  them 
upon  porous  plaster  tiles.  The  crystals  are  then  dissolved  in  ether, 
the  solution  again  mixed  with  some  ligroin,  freed  from  the  deposited 
oily  matter,  and  evaporated  spontaneously.  Repeated  recrystalliza- 
tion  from  ether  yields  larger  but  still  yellow  ci-ystals,  which  are  ob- 
tained white  by  dissolving  them  in  alcohol  and  adding  water  until 
a  permanent  precipitate  begins  to  appear. 

Ostruthin  crystallizes  from  ether  in  the  triclinic  system,  the  cry- 
stals resembling  rhombohedrons.  It  fuses  at  115°  C,  and  congeals  at 
91°  C.  to  a  wax-like  mass,  becoming  crystalline ;  it  is  inodorous, 
tasteless,  burns  with  a  bright  smoky  flame,  and  yields  by  dry 
distillation  a  thick  yellowish  oil,  with  an  odour  resembling  Canada 
balsam.  It  is  insoluble  in  cold  water,  sparingly  soluble  in  benzol 
and  petroleum  benzin,  and  freely  soluble  in  alcohol  and  ether.  The 
alcoholic  solution  has  a  faint  blue  fluorescence,  which  becomes  mag- 
nificently blue  on  the  addition  of  water ;  more  water  precipitates  it. 
All  its  solutions  are  neutral  and  optically  inactive.     It  composition  is 

Ostruthin  hydrochlorate,  C^^  H^^  Oo  H  CI,  is  obtained  by  passing 
muriatic  acid  gas  into  a  not  very  dilute  alcoholic  solution  of  os- 
truthin, which  congeals  ;  the  mass  is  then  washed  with  water  and 
crystallized  from  ether.  It  forms  white,  tasteless,  and  inodorous 
needles,  soluble  in  alcohol,  ether,  benzol,  and  chloroform  ;  less  so  in 
petroleum  benzin. 


98  YEAR-BOOK    OF    PIIARMACV. 

Ostrutliin  hydrobromate  is  prepared  in  the  same  way  ;  but  in 
attempting  to  crystallize  from  ether  it  was  decomposed,  bromine 
being  liberated.  A  combination  with  hydriodic  acid  could  not  be 
obtained,  owing  to  the  liberation  of  iodine.  Among  the  products  of 
decomposition  obtained  by  adding  ostruthin  to  fusing  potash, 
resorcin  was  found.  Treated  with  strong  nitric  acid,  it  is  first  con- 
verted in  a  resinous  body,  and  finally  into  oxalic  acid ;  but  when 
boiled  for  a  long  time  with  nitric  acid,  diluted  with  three  parts  of 
water,  it  yields  styphinic  and  a  little  oxalic  acid. 

Chlorine  yields  with  difficulty,  bromine  more  readily,  substitution 
compounds. 

Volumetric  Estimation  of  Astringent  Principles.  F.  Jean.  (Compt. 
Bend.,  Ixxxii.,  0S2.)  Tannic  and  gallic  acids,  and  other  astrin- 
gent substances,  after  the  addition  of  an  akaline  carbonate,  ener- 
getically absorb  iodine  from  its  solution ;  and  this  absorption  takes 
place  in  direct  proportion  to  the  quantity  of  the  astringent  matter 
present.  For  the  estimation  of  such  substances  the  author  employs 
a  0'4  per  cent,  solution  of  iodine  in  potassium  iodide,  and  this  is 
titrated  by  means  of  a  standard  solution  of  tannin  in  sodium  car- 
bonate. Under  the  influence  of  the  iodine  the  tannin  solution 
acquires  an  intense  orange  red  colour,  which  would  prevent  the 
starch  test  being  applied  as  an  indicator  of  the  presence  of  free  iodine, 
if  this  test  were  applied  in  the  ordinary  way.  But  the  author  rubs 
powdered  starch  over  white  filter-paper,  and  when  a  minute  drop  of 
the  deeply  coloured  liquid  is  placed  on  the  paper,  it  is  instantly 
absoi'bed,  while  the  characteristic  violet  stain  due  to  the  free  iodine 
remains.  As  decoction  of  oak  bark  is  found  to  contain  no  principle 
other  than  tannin,  which  is  capable  of  exercising  this  action  on 
iodine,  the  method  is  directly  available  for  testing  barks  intended 
for  tanning  purposes. 

Ferric  and  Aluminic  Phosphates.  M.  Millot.  {Journ.  Chem. 
Soc,  from  Comptes  Rendus,  Ixxxii.,  89.) 

Ferric  Fhosphite.—2  P.  O5.  Fco  O3.  8  H.  0  =  Fe.  P.^  Oj^.  8  Ho  0.— 
This  phosphate  is  obtained  when  ferric  hydrate  or  oxide  is  dissolved 
in  hydrated  phosphoric  acid,  either  cold  or  hot.  If  an  insufficient 
quantity  of  phosphoric  acid  is  employed,  the  mass  hardens,  and 
more  phosphoric  acid  must  be  added  till  it  remains  pasty.  Water 
is  added  and  the  liquid  is  filtered.  On  addition  of  water  to  the 
washings,  the  phosphate,  :3  Po  0-.  2  Fe^  O3.  8  Ho  0,  is  deposited. 
The  mass  left  on  the  filter,  after  purification,  has  the  formula, 
•1  Po  Oj.  Fco.  O3. 8  Ho  O. 

The   anhydrous  <6alt  is  prepared  by  fusing  ferric  oxide  with  an 


PHARMACEUTICAL    CHEMISTRY.  09 

exc3ss  of  phosplioric  acid,  and  removing  tlie  excess  by  wasliing.  If 
a  liigli  temperature  be  employed,  part  of  the  product  becomes 
insoluble  in  acids,  but  docs  not  vary  in  composition  from  the 
portion  which  dissolves.  The  hydrated  phosphate  dissolves  in 
ammoniacal  ammonium  citrate,  and  in  alkalies  and  their  carbonates, 
but  is  insoluble  in  acetic  acid.  The  precipitate  obtained  on  adding 
water  to  the  filtrate  from  the  preparation  of  the  above-mentioned 
phosphate  is  white  and  crystalline.  Its  formula  is  3  Po  0,-.  2  Fe^  0-. 
8  Ho  0  =  Fe^  Pg  Oo]^.  8  Ho  0.  It  is  more  easily  prepared  by  heating 
a  solution  of  ferric  sulphate  with  dihydi'ic  ammonia  orthophosphate, 
thus  : — 
0.  (N  H,)  H.  P  Oi  +  2  Fe.  (S  OJ3  =  Fe^ P^  0.^. H,  0  +  6  (N HJ  H  S  0^. 

The  liquid  is  filtered  white  hot,  and  the  precipitate  is  washed 
with  boiling  water.  When  ignited  it  turns  to  a  greyish  blue  mass, 
which  dissolves  easily  in  acids.  Its  properties  are  similar  to  the 
preceding  one. 

Aluminlc  PhospJiate—-2  P,  0  5.  Ah  O3.  8  H.  0  =  Al.  P.^  0^3.  8  H.  0. 
— This  salt  cannot  be  prepared  in  the  same  manner  as  tlie  corre- 
sponding iron  salt,  owing  to  the  solubility  of  alumina.  It  may  be 
obtained  by  treating  the  phosphate,  Al^  Pg  Oo^.  16  H,  0,  with  two 
equivalents  of  phosphoric  acid ;  it  is  dried,  washed,  and  the  treat- 
ment repeated.  It  may  be  obtained  in  the  anhydrous  state  by 
igniting  a  salt  of  alumina  with  excess  of  phosphoric  acid,  and  wash- 
ing out  the  metaphosphoric  acid  formed,  with  water.  The  product 
is  partially  insoluble  in  acids. 

3  P.  O5.  2  AL  O3. 16  H,  O  =  Alt  Pg  O^i.  16  H.  0. 
This  phosphate  is  obtained  when  two  equivalents  of  aluminum 
sulphate  and  six   equivalents  of    dihydroammonic   orthophosphate 
are  boiled  together,  thus  : — 
2  Al.  (S  0^)3  +  6  Ho(NHJP  0,i  =  AljPg  Ooi-  3H.0  +  3(NH,)HS0j. 

The  precipitate  is  filtei'ed  and  washed  with  boiling  water,  for  it 
is  soluble  in  cold  water.  Free  sulphuric  acid  must  be  present 
during  its  preparation,  or  it  will  contain  excess  of  alumina.  This 
salt  is  formed  when  commercial  superphosphates  are  washed  with 
water.     When  ignited  it  becomes  partially  insoluble  in  acids  : — 

2  P.  O5  3  AI3  O3.  8  H,  0  =  Alg  P^  O19. 8  H^  0. 

If  an  acid  solution  of  one  of  the  previously- described  phosphates 
is  precipitated  with  ammonia,  taking  care  not  to  add  sufiicient  to 
■dissolve  it,  this  phosphate  is  produced.  When  ignited  it  dissol,vcs 
.in  acids. 


100  YEAK-BOOK    OF    PHARMACY. 

All  these  phosphates  are  hygroscopic ;  they  are  all  insoluble  in 
acetic  acid,  but  dissolve  in  ammoniacal  ammonium  citrate,  am- 
monium oxalate,  alkaline  carbonates,  and  ammonia ;  tliose  of 
alumina  dissolve  much  more  easily  than  the  correspondin<:^  iron 
salts. 

A  Hydrate  of  Cellulose.  A.  Girand.  (Zeitschr.  dos  oesterr. 
A^oth.  Ver.,  187(3,  557,  from  Coinptes  licndus.)  Besides  the  normal 
cellulose  as  it  is  obtained  from  the  oi'gans  of  i)lants,  and  the  gela- 
tinous modification  of  the  same  mentioned  by  Bechamp  in  1856, 
there  is  known  to  exist  another  peculiar,  not  very  distinctly  charac- 
terized variety  of  this  substance,  the  formation  of  which  is  frequently 
observed  in  industrial '  operations.  The  celhilose  in  this  state 
appears  to  have  lost  its  firmness  and  become  friable.  In  submitting 
this  body  to  a  closer  examination,  the  author  recognised  it  as  the 
first  modification  produced  from  cellulose  by  the  action  of  acids. 
In  preparing  it  the  conditions  requisite  for  its  formation  must  be 
scrupulously  observed  ;  the  acid  must  be  of  a  definite  strength,  and 
must  be  allowed  to  act  on  the  cellulose  at  a  definite  temperatui'e 
and  for  the  exact  time  required.  Pure  cotton  wool  is  moistened 
with  water,  then  introduced  into  cold  sulphuric  acid  of  1"450 
specific  gravity,  and  left  in  contact  with  it  for  about  12  hours.  At 
the  expiration  of  this  time  the  fibres  appear  but  little  altered,  but 
when  pressed  between  two  glass  plates  they  break  up  into  a  multi- 
tude of  small,  iiTCgular  fragments.  Notwithstanding  its  friability, 
this  substance  can  be  readily  washed  and  dried  at  a  low  tempe- 
rature without  losing  its  shape.  In  the  dry  state,  however,  it 
crumbles  between  the  fingers  to  a  fine  snow-like  powder.  The 
numbers  obtained  in  its  ultimate  analysis  lead  to  the  formula 
Ci2  Hoj  ^11'  ""^hich  represents  it  as  a  monohydrated  cellulose.  It 
does  not  part  with  its  molecule  of  water  on  drj-ing. 

Hydrocellulose,  as  the  author  calls  this  substance,  possesses 
definite  characteristic  properties.  It  is  readily  oxidizable  ;  heated 
to  50°  C.  for  several  days  it  gradually  turns  yellow,  while  its  per 
centage  of  oxygen  increases  and  that  of  its  carbon  diminishes.  If 
it  now  be  washed  with  water,  it  yields  to  the  latter  a  coloured 
substance  which  reduces  both  Fehling's  solution  and  silver  nitrate ; 
but  the  insoluble  residue  is  nothing  but  unaltered  hydrocellulose, 
Ci2  Hot  Oj|.  Heated  with  a  1  per  cent,  solution  of  caustic  potash  it 
is  gradually  dissolved,  with  the  formation  of  a  strongly  coloured 
liquid  possessing  reducing  properties. 

The  formation  of  a  friable  hydrocellulose  as  an  intermediate 
product  between  cellulose  and  glucose   seems  to   throw  light  on. 


rHAEMACEUTICAL   CHEMISTRY.  101 

certain  industrial  processes  which  were  hitherto  but  little  under- 
stood. The  production  of  parchment  paper,  for  instance,  may  be 
attributed  to  a  superficial  conversion  of  the  paper  fibre  into  hydro- 
eelhilose.  These  fibres  adhere  closely  and  firmly  together,  thus 
closing  the  pores  of  the  paper  and  making  it  impermeable.  If  the 
action  of  the  acids  is  allowed  to  proceed  too  far,  or  if  the  washing  is 
done  imperfectly,  the  whole  of  the  fibres  are  then  changed  in  this 
manner,  and  the  paper  becomes  flawy.  Possibly  the  mellowing  of 
paper  and  of  cloth,  due  to  an  imperfect  removal  of  the  bleaching 
agents  by  washing,  may  also  be  explained  as  the  result  of  the  for- 
mation of  hydrocellulose.  The  chlorinated  lime,  being  decomposed 
by  the  carbonic  acid  contained  in  the  air,  forms  hypochlorous  and 
hydrochloric  acid,  by  the  action  of  which  on  the  cellulose  the  latter 
may  be  pai-tially  convei'ted  into  hydrocellulose. 

The  Constituents  of  Balsam  of  Toln.  E.  Busse.  (Ber.  der 
deutscli.  Chem.-Ges.  ix.,  830;  Journal  Chemical  Societij.  Dec,  ISTC? 
640.)  Somewhat  contradictory  results  have  been  arrived  at  by 
Fremy,  Deville,  Kopp,  Scharling,  and  Carles,  partly  at  least  due  to 
the  fact  that  the  mode  of  operating  was  calculated  in  some  cases  to 
bring  about  decomposition  of  the  bodies  originally  present.  The 
author  dissolved  1  kilo,  of  partly  resinized  tolu  balsam  in  '2  litres 
of  ether,  filtered  the  liquid  from  a  little  insoluble  matter,  and  then 
agitated  it  with  2  litres  of  soda-solution  containing  100  grams 
Na^  0 ;  after  agitating  the  ethereal  liquor  again  with  soda,  and 
washing  with  water,  a  residue  was  obtained  on  distilling  off  the 
ether,  consisting  of  85  grams  of  fluid  neutral  compounds.  On 
fractional  distillation,  a  little  passed  over  below  200°,  more  between 
250°  and  300°,  and  most  of  all  above  320°.  The  first  of  these 
fractions  appeared  on  analysis  to  be  impure  benzylic  alcohol ;  it 
formed  benzoic  aldehyde  and  acid  on  oxidation.  The  second  gave  a 
distillate  at  300^,  consisting  of  henzijl  henzoate,  Ci^HjoOj;  on 
saponification  it  formed  benzylic  alcohol  and  a  benzoate.  The 
third  poi'tion  consisted  of  benzijl  cinnamate,  Cj(;H;^jOo;  it  furnished 
cinnamic  acid  and  benzylic  alcohol  on  saponification,  and  had  the 
sp.  gr.  1-1145  at  16°.  Hence  the  natural  constituents  of  tolu  balsam 
are  the  same  as  those  found  by  Kraut  in  Peru  balsam,  only 
they  exist  in  smaller  quantity  and  difierent  proportions, — benzyl 
cinnamate  forming  the  majority  in  the  first,  benzyl  benzoate  in  the 
second. 

The  soda  liquors  obtained  as  above  described  were  saturated  with 
carbonic  acid,  whereby  much  resin  was  precipitated.  The  filtx'ate 
yielded  a  precipitate  on  addition  of  hydrochloric  acid;  one-half  of 


102 


YEAR-BOOK    OF    PHARMACY. 


the  cinnamic  acids  thus  throvi-n  down  -was  boiled  with  milk  of  lime. 
A  sparingly  soluble  lime  salt  was  thus  obtained,  containing  (after 
recrjstallization)  1026  per  cent,  of  calcium,  the  cinnamate  requiring 
10"30  per  cent. ;  fi-om  this  cinnamic  acid,  melting  at  133°,  was 
isolated.  The  mother-liquors  of  the  sparingly  soluble  calcium 
cinnamate  contained  much  calcium  benzoate,  which  crystallized  out 
after  concentration  ;  this  gave  (after  several  recrystallizations)  num- 
bers agreeing  with  the  formula  Ca  (C^  B.-  0^)o  +  3  H^  0  ;  and  from  it 
benzoic  acid  was  precipitated,  melting  at  120"5°. 

The  other  half  of  the  mixture  of  acids  was  dissolved  in  alcohol 
and  treated  with  hydrochloric  acid  gas.  By  fractional  distillation 
the  ethers  thus  formed  were  separated ;  the  portion  distilling  at 
215^  gave  numbers  agreeing  with  the  foi-mula  Cg  H^q  O3,  ethyl 
benzoate;  that  passing  over  at  265°  agreed  with  Cj^HijO.,,  ethyl 
cinnamate. 

Hence  tolu  balsam  contains  free  benzoic  and  cinnamic  acids,  as 
well  as  their  benzylic  ethers. 

Determination  of  Phosphorus  and  Arsenic  by  Molybdate  of 
Ammonia.  P.  Champion  and  H.  Pellet.  {Bull,  de  la  Soc. 
Chim.,  January  o,  1877;  Chem.  News,  3-5,  11-5.)  M.  Boussingault 
has  shown  that  the  ajiproximation  furnished  by  directly  weighing 
the  phospho-molybdate  is  superior  to  that  obtained  by  redissolving 
the  precipitate  and  determining  the  phosphorus  as  ammoniaco- 
magnesian  phosphate.  The  error  committed  is  the  more  appreci- 
able the  less  phosphorus  is  present  in  the  matter  under  analysis. 
According  to  M.  Boussingault  the  phospho-molybdate  contains  3' 73 
pel*  cent,  of  phosphoric  acid.  The  operation  may  be  performed 
very  rapidly  by  observing  the  following  precaiitions  : — Dissolve 
100  grams  molybdic  acid  in  ammonia  (about  loO  c.c.  of  ordinary 
ammonia)  and  80  of  water.  Pour  it  drop  by  drop  into  oOO  c.c.  of 
pure  nitric  acid  and  300  c.c.  of  water.  Stir,  let  settle,  and  filter  if 
needful.  Introduce  into  a  capsule  such  a  measure  of  the  molybdic 
solution  that  the  weight  of  the  molybdic  acid  may  be  about  fifty 
times  the  supposed  weight  of  the  phosphoric  acid.  Add  ammonia 
to  render  the  liquid  alkaline ;  concentrate  as  far  as  possible  the 
liquid  containing  the  phosphoric  acid,  and  mix  the  two  solutions  ; 
raise  the  temperature  to  70°  to  80°,  and  pour  in  rapidly  an  excess 
of  nitric  acid  until  the  yellow  coloration  appears,  stirring  briskly 
to  aid  the  formation  of  the  pi'ccipitate.  Filter  through  a  double 
tared  filter,  wash,  and  dry  at  100°  to  110°.  The  filtrate  should  be 
colourless.  If  it  is  yellow,  the  precipitation  is  incomplete ;  in  this 
case  ammonia  is  poured  upon  the  filter  to  redissolve  the  precipitate, 


PHAEMACEUTICAL    CHEMISTKY.  105 

the  solution  is  evaporated,  and  re-acidified  witli  nitric  acid.  The 
same  process  may  be  successfully  applied  to  the  determination  of 
arsenic,  100  grams  of  the  precipitate  of  arsenio-molybdate  of  am- 
monia containing  o'l  of  arsenic  acid. 

Compounds  of  Metallic  Oxides  with  Glycerin.  J.  Puis.  (Journ. 
fill'  pract.  Chem.,  No.  2,  1877.)  The  author  describes  an  extensive 
series  of  experiments  on  the  solubility  of  various  metallic  oxides 
in  glycerin,  performed  by  adding  aqueous  solutions  of  metallic  salts 
to  mixtures  of  glycerin  and  H  K  0.  Clear  solutions  were  obtained 
when  glycerin,  ferric  oxide,  and  caustic  potash  were  in  the  mole- 
cular proportions  of  3:2:1  and  3:3:2.  After  a  short  lapse  of 
time  the  ferric  oxide  is  precipitated  spontaneously  from  the  solu- 
tions, and  has  passed  into  the  colloidal  state.  Cupric  oxide  does 
not  show  this  peculiarity.  With  weak  solutions  of  glycerin  the 
water  appears  to  exert  a  neutralizing  influence  upon  the  base 
present,  which  allows  the  solution  of  the  oxide  ;  but  after  a  certain 
degree  of  concentration  there  is  a  fixed  relation  between  the 
weights  of  glycerin  and  Cu  0  dissolved.  The  author  recommends 
the  application  of  this  fact  for  the  analytical  determination  of 
glycerin.  The  hydrates  of  the  alkaline  earths  are  much  more 
soluble  in  glycerin  than  the  oxides  of  the  heavy  metals. 

Titration  of  a  Mixture  of  Alkaline  and  of  Earthy  Alkaline  Sul- 
phates. F.  Jean  and  H.  Pellet.  (Bull,  de  la  Soc.  Ghim. ;  Chem. 
Neios,  35,  152.)  Let  there  be  a  mixture  formed  of  sulphates  of 
potassa,  soda,  lime,  magnesia,  and  of  alkaline  and  alkalino-earthy 
chlorides  and  nitrates.  It  is  required  to  determine  the  sulphuric 
acid  combined  with  alkalies  and  the  sulphates  of  lime  and  magnesia. 
These  determinations  may  be  easily  and  exactly  obtained  by  the  use 
of  two  standard  liquids, — the  one  of  sulphuric  acid,  the  other  carbo- 
nate of  soda,  by  operating  in  the  following  manner  : — 

1.  Titration  of  Sidplmric  A cid  covib inecl  loitli  Alkaloids. — The  matter 
being  dissolved  in  water  (or  in  water  acidulated  with  hydrochloric 
acid,  if  necessary)  is  exactly  neutralized  with  soda  in  a  diluted  so- 
lution. To  a  volume  of  the  liquid  to  be  analysed  we  add  a  slight 
excess  of  baryta  water,  then  seltzer  water,  and  boil  it  to  drive  away 
completely  the  excess  of  carbonic  acid,  and  to  render  insoluble  all 
the  carbonate  of  baryta.  We  filter,  and  pour  into  the  clean  liquid, 
coloured  with  a  few  drops  of  tincture  of  litmus,  standard  sulphuric 
acid  to  neutralization.  The  quantity  of  sulphuric  acid  employed  to 
saturate  the  alkali  is  exactly  the  same  as  that  which  was  originally 
combined  with  the  alkalies,  potash  and  soda. 

2.  Titration  of  Sulphate  ofLitne. — A  volume  of  the  saline  solution 


104i  YEAR-BOOK    OF   PHARMACY. 

is  mixed  witli  alcoliol ;  the  sulphate  of  lime  precipitated  is  collected 
on  a  filter,  washed  with  alcoholic  water,  then  introduced  into  a 
Bohemian  glass,  or  into  a  capsule,  with  a  known  volume  of  a 
standard  solution  of  carbonate  of  soda.  "We  raise  it  to  a  boil,  then 
separate  by  filtration  the  carbonate  of  lime  arising  from  the  decom- 
position of  the  sulphate.  In  the  filtered  liquid  we  titi-ate  the  car- 
bonate of  soda  remaining ;  and  we  have  by  the  diifereuce  the 
quantity  of  this  salt  passed  into  the  state  of  sulphate  of  soda,  which 
is  calculated  as  sulphate  of  lime. 

3.  Titration  of  Sulphate  of  Magnesia. — The  solution  to  be  analysed 
is  treated  at  a  boil  with  a  known  volume  of  a  standard  solution  of 
carbonate  of  soda.  We  separate  by  filtration  the  carbonate  of  lime 
and  magnesia  ;  and  we  determine  in  the  filtered  liquid,  by  the  aid  of 
standard  sulphuric  acid,  the  quantity  of  soda  not  decomposed,  whence 
we  calculate  the  amount  of  sulphuric  acid  belonging  to  the  sulphate 
of  lime  and  magnesia.  The  weight  of  the  sulphate  of  lime  being 
given  by  the  preceding  operation,  we  find  by  the  difference  that  of 
sulphate  of  magnesia. 

4.  Determination  of  total  Sulpliuric  Acid. — If  in  a  mixture  of  salts 
we  wish  to  titrate  total  sulphuric  acid,  free  and  combined,  we  boil 
the  solutions  with  carbonate  of  soda,  we  separate  the  carbonate 
of  magnesia  and  lime,  and  the  liquid,  filtered  after  having  been 
exactly  neutralised  with  standard  sulphuric,  is  treated  with  baryta 
water,  as  in  the  titration  of  alkaline  sulphates.  This  method  of 
tritration  gives  vei'y  exact  results  when  Ave  employ  a  solution  of 
sulphuric  acid  sufliciently  dilute.  Thus,  in  a  mixture  of  salts  con- 
taining total  sulphuric  acid  OG-A-i  gram,  Ave  have  found  by  our 
process  0'663  gram  ;  and  in  0'112  gram  of  sulphate  of  potash 
O'llO  gram. 

Estimation  of  Theine  in  Tea.  M.  Markownikoff.  (Ber.  der 
deutsch.  Chem.-Ges.,  ix.,  lol'i.)  15  grams  of  powdered  tea  leaves  are 
boiled  Avith  500  grams  of  water  and  15  grams  of  calcined  magnesia 
for  some  time ;  the  decoction  is  filtered,  the  residue  Avell  washed, 
and  the  filtrate,  together  with  the  washings,  evaporated,  with  the 
addition  of  a  little  calcined  magnesia,  to  perfect  dryness.  Upon 
exhausting  the  dry  residue  Avith  hot  benzol,  filtering,  and  evapo- 
rating the  filtered  solution,  the  theine  is  obtained  iu  a  pure  state. 

Coffee  may  be  submitted  to  the  same  process. 

Action  of  Hydrochloric  Acid  on  Potassium  Chlorate.  G .  S  c  h  a  c  k- 
erl.  {Liehic/s  Annalen,  clxxxii.,  ID.j ;  Journ.  Chcm.  Soc,  1877,  47.) 
Pebal  showed  that  the  action  of  hydrochloric  acid  on  potassium 
chlorate  results  iu  the  formation  of  chlorine  and  hypochloric  acid 


PHAEMACEDTICAL   CHEMISTRY. 


105 


(CI  O2)  in  varying  proportions.  The  author's  experiments  on  this 
subject  have  led  to  the  conclusion  that  the  action  is  represented 
primarily  by  the  equation  : — 

K  CI  O3  +  2  H  CI  =  CI  Oo  +  CI  +  K  CI  +  H,  0 ; 

or,  when  sulphuric  acid  and  potassium  chloride  are  employed,  by 
the  equation, — 

KC103  +  KCl  +  2H2S04=C10,  +  Cl  +  2KHS04  +  HoO; 

but  that,  in  most  cases,  there  occurs  a  secondary  action  of  free  hy- 
drochloric acid  first  formed,  whereby  the  pi'oportion  of  chlorine  is 
increased.  The  extent  to  which  this  secondary  action  takes  place 
was  found  to  depend  upon  the  amount  and  strength  of  the  hydro- 
chloric acid  present  in  the  liquid  from  which  the  gases  were  evolved. 
Thus,  when  a  solution  of  potassium  chlorate  was  run  into  hot  hy- 
drochloric acid  of  sp.  gr.  1*19,  the  proportion  by  volume  of  the 
hypochlorous  acid  and  chlorine  evolved  was  2/35"6  ;  bat  when  finely 
triturated  potassium  chlorate  was  decomposed  with  hydrochloric 
acid  diluted  with  twice  its  bulk  of  water,  the  two  gases  were  in  the 
proportion  of  2/l"71.  Again,  when  a  mixture  of  1  molecule  of  potas- 
sium chlorate  and  0  molecules  of  potassium  chloride  was  decomposed 
by  sulphuric  acid,  the  hypochlorous  acid  and  chlorine  were  evolved 
in  the  proportion  of  2/5"54  ;  but  when  a  mixture  of  4  molecules  of 
chlorate  and  1  molecule  of  chloride  was  decomposed  in  the  same 
mannei',  the  two  gases  were  in  the  proportion  of  2/l"27.  Numerous 
other  experiments  were  made,  all  leading  to  the  same  conclusion.  In 
no  case  was  pure  chlorine  obtained.  The  gases  were  analysed  by 
Pebal's  method. 

Purification  of  Oleic  Acid.  L.  "Wolff,  (Neiv  Remedies,  from 
Amer.Journ.  Pharm.)  The  author  proposes  the  following  method  of 
obtaining  oleic  acid  of  sufiicient  purity  to  prepare  the  oleates  at 
present  in  use  : — Oil  of  sweet  almonds  is  saponified  with  caustic  po- 
tassa  ;  the  soap  is  decomposed  with  tartaric  acid,  and  washed  with 
hot  water  to  separate  the  precipitated  potassium  bitartrate  from  the 
mixture  of  oleic  and  palmitic  acids.  These  are  combined  with 
litharge,  forming  oleo-palmitate  of  lead,  from  which  petroleum 
benzin  dissolves  the  oleate  of  lead,  leaving  the  other  salt  as  a  resi- 
due. From  the  benzin  solution  the  lead  is  precipitated  by  dilute 
hydrochloric  acid,  in  form  of  lead  chloride  ;  and  on  evaporation  of 
the  benzin,  oleic  acid  will  remain,  sufficiently  pure  for  pharma- 
ceutical purposes,  giving  clear  and  permanent  solutions  with  the 
red  and  yellow  varieties  of  mercuric  oxide,  as  high  as  30  per  cent,  if 
necessary.     As  crude  commercial  oleic  acid  can  be  bought  at  very 


106 


YEAR-BOOK    OF    PHARMACY. 


low  figures,  this  may  be  made  the  stai'fcing-point  of  the  process, 
yielding  a  purified  acid  at  a  very  small  expense.  To  gain  the  same 
end,  the  simplest  way  is  perhaps  to  use  the  ready-made  oleo-palmi- 
tate  of  lead, — the  officinal  lead-plaster, — to  dissolve  it  in  benzin,  and 
extract  from,  it  the  oleic  acid  by  precipitating  the  lead  by  hydro- 
chloric acid.  Oleic  acid  thus  prepared  has  been  used  for  some 
time,  and  found  to  answer  better  for  the  preparation  of  the  oleates, 
tlian  the  article  sold  by  some  of  the  manufocturing  chemists. 

Determination  of  Albumen  in  Urine.  J.  Stolnikow.  (Chem. 
Centralbl.)  The  urine  is  diluted  with  water,  until  a  sample  poured 
upon  some  nitric  acid  contained  in  a  test-tube  pi'oduces  still  a  faint 
white  ring  at  the  point  of  contact  after  the  lapse  of  forty  seconds. 
The  number  of  volumes  of  water,  added  to  the  volume  of  the  urine 
(which  may  be  taken  as  1),  is  divided  by  250,  and  the  quotient  will 
be  the  percentage  of  albumen  in  the  urine.  This  relation  has  been 
established  and  confirmed  by  gravimetric  determinations. 

Soap  Analysis.  (From  CImyi.  News,  :^xxv.,  2.)  Weighing. — In  all 
methods  usually  given  in  text  books  the  analyst  is  dii'ected  to  weigh 
out  for  each  operation  small  portions  (1  to  5  grams)  of  the  sample. 
This  plan  is  to  be  avoided,  and  for  two  reasons: — (1)  Soap  is  ex- 
tremely variable  in  composition,  and  considerable  variations  are  pos- 
sible even  in  the  same  sample  ;  (2)  it  is  perpetually  losing  water 
by  evaporation  from  its  surface.  As  the  soap  is  usually  weighed  in 
the  form  of  thin  shavings,  the  surface  exposed  is,  in  relation  to  the 
weight  taken,  very  considerable.  These  two  sources  of  inaccuracy 
are  obviated  by  weighing  out  for  the  analysis  a  section  cut  through 
the  bar  at  right  angles  to  its  length  (GO  to  80  grams),  dissolving  in 
distilled  water,  and  making  the  volume  up  to  1000  c.c.  (in  the  cold) ; 
oO  c.c.  of  this  solution  are  measured  off  for  this  operation.  It  should 
be  observed,  that  as  some  of  the  alkaline  salts  of  the  fatty  acids 
separate  out  from  the  solution  on  cooling,  it  must  be  well  mixed  by 
agitation  previously  to  drawing  off  each  50  c.c.  The  several  opera- 
tions are  conducted  as  follows:  — 

1.  Total  Alhidi. — 50  c.c.  of  the  solution  are  diluted  to  about 
200  c.c,  the  liquid  is  coloured  faintly  with  eosine,  and  standard  acid 
is  run  in,  taking  care  to  stir  briskly  Avith  a  glass  rod.  The  neutral 
point  is  extremely  well  marked  by  the  suddeu  decolorization  of  the 
whole.  The  cause  of  this  apparent  destruction  of  colour  is  the  union 
of  the  fatty  acids  with  the  eosine  at  the  moment  of  their  complete 
separation  from  the  fluid. 

2.  Uiicomhined  Alkali. — 50  c.c.  ai*e  added  to  300  c.c.  of  a  satura- 
ted solution  of  common  salt,  which  must  be  of  course  neutral  to  test 


PHARMACEUTICAL    CHEMISTRY.  107 

paper,  and  the  volume  made  up  to  400  c.c.  The  neutral  alkaline 
salts  of  the  fatty  acids  (i.e.,  true  soap)  are  preci[)itated ;  any  excess 
of  alkali  present  remains  in  solution, — this  is  determined  in  an  ali- 
quot part  of  the  filtered  solution.  The  filter  must  not  be  moistened 
previous  to  filtration.  From  this  the  total  uncombined  alkali  is 
calculated,  and  subti-acted  from  the  total  alhall  already  found.  Then 
the  combined  and  luicomhiiicd  alkali  are  determined. 

3.  Fatty  Acids. — 50  c.c.  of  this  solution  are  introduced  into  a 
stoppered  separating  funnel,  decomposed  with  excess  of  acid,  and 
agitated  with  carbon  disulphide  until  the  libei-ated  fatty  acids  are 
dissolved.  The  disulphide  solution  of  the  fats  is  di-awn  off  into  a 
tared  flask  ;  the  aqueous  solution  is  washed  once  or  twice  with  small 
portions  of  disulphide,  the  whole  of  which  is  then  separated  from 
the  fats  by  distillation.  The  fats  are  purified  from  the  last  traces 
of  C  Sj  by  heating  the  flask  for  a  short  time  at  100°  C. ;  the  weight, 
after  cooling,  less  the  tare,  gives  the  weight  of  the  fatty  acids.  Or- 
dinary ether  may  be  used  in  place  of  the  C  So ;  it  has,  however,  the 
disadvantage  of  retaining  small  quantities  of  water,  and  therefore 
aqueous  acids,  which  must  be  driven  off"  at  the  end  of  the  operation 
by  exposing  to  a  temperature  of  100  °  to  120°  C,  until  the  weight  is 
constant.  Further,  the  ethereal  solution  will  be  the  upper  stratum, 
and  is,  for  obvious  reasons,  not  so  easily  to  be  manipulated  as  the 
bisulphide  solution,  which  forms  the  lower  layer. 

Note. — A  moment's  consideration  of  the  following  equation,  repre- 
senting the  composition  of  sodic  cleate  by  H  CI — 

2 1  Cis  ^3|ONo  +  2  H  CI  =  2  Na  CI  +  2  I  ^^^  ^^s  ^No, 

will  make  it  evident  that  while  the  fiitty  acid  is  present  in  the  soap 
in  the  form  of  anhydride,  it  is  separated  and  weighed  in  the  course 
of  analysis  as  hydrate.  A  correction  must,  therefore,  be  applied, 
based  upon  the  fact  that  282  parts  oleic  hydrate  equal  273  parts 
oleic  anhydride;  i.e.,  the  weight  of  the  fatty  acids  is  to  be  multiplied 
by  the  decimal  fraction  007. 

In  the  case  of  the  "  olein  "  soap  of  commerce,  a  very  rapid  and 
tolerably  accurate  estimation  may  be  made  in  the  following  way  : — 
50  c.c.  of  the  solution  are  decomposed  with  H  CI  in  a  small  flask,  the 
neck  of  which  is  long  and  narrow,  and  graduated  in  c.c,  and  so  much 
water  added  that,  upon  heating  in  the  water  bath  the  separated  oil 
will  rise  into  the  neck  and  fall  entirely  within  the  graduated  portion. 
The  heating  must  be  continued,  with  occasional  tapping  of  the  flask, 
until  the  whole  of  the  fat  has  been  separated  and  has  risen  into  the 
neck. 


108 


YEAK-BOOK    OF    PUAUMACT. 


The  flask  is  allowed  to  cool,  and  when  cool  the  volume  of  the  oil 
is  read  off.  This  quantity,  multiplied  by  the  specific  gravity  of  the 
oil,  gives  its  weight.  The  specific  gravity  (which  the  writer  almost 
always  found  to  be  0'9)  may  be  determined  by  pouring  off  a  small 
quantity  into  a  capsule  (a  second  reading  will  give  the  volume 
taken),  and  weighing  it ;  the  weight  divided  by  the  volume  is  the 
required  specific  gravity. 

4.  Wafer. — If  the  purity  of  the  sample  has  been  ascertained,  this 
constituent  may  be  calculated  by  difference.  The  direct  estimation 
is  effected  by  evaporating  50  c.c.  of  the  solution  to  dryness  on  the 
water  bath  (finally  on  the  air  bath  from  100°  to  120°  C.)  in  a  Aveighed 
dish.  The  residue  is  anhydrous  soap ;  from  its  weight  the  per- 
centage of  water  on  the  soap  may  readily  be  calculated.  It  may  be 
observed  that  the  usual  method,  which  consists  in  the  exposure  of 
the  soap,  previously  cut  into  thin  shavings  and  weighed,  to  the 
temperature  of  boiling  water  until  it  ceases  to  lose  weight,  is  in- 
accurate, as  it  fails  to  drive  off  the  last  portions  of  water  (1  to  2  per 
cent.),  which  seem  to  have  contracted  a  stronger  union  with  the  soap. 

5.  Mineral  Impurities  and  TJnsaponified  Fat  may  be  detected  by 
taking  the  dried  soap  from  the  preceding  operation,  dissolving  in 
strong  alcohol,  and  filtering  through  a  funnel  heated  by  means  of  a 
jacket  of  hot  water.  Mineral  impurities  remain  upon  the  filter  as 
an  insoluble  residue,  the  weight  of  which  is  readily  ascertainable. 
The  alcoholic  filtrate  is  evaporated  with  successive  additions  of  dis- 
tilled water ;  by  these  means  any  unsaponified  fat  or  resin  is  separa- 
ted from  the  soap,  which  of  course  remains  in  aqueous  solution. 
This  solution  may  be  used  for  N'o.  1,  2,  or  3.  The  mineral  impurities 
may  be  examined  qualitatively  after  drying  and  weighing. 

Preparation  of  Potassium  Bicarbonate.  L.  Pesci.  (Journ.  Chem. 
Soc,  Oct.,  1876,  381.)  The  author  finds  that  the  best  method  of 
preparing  pure  potassium  bicarbonate,  free  from  chloride  and  nitrate, 
is  to  pass  a  current  of  carbonic  anhydride  to  saturation  though  a 
solution  of  potassium  hydrate  in  alcohol  of  80  per  cent.  At  first 
neutral  carbonate  is  formed,  which  withdraws  the  water  from  the 
alcohol,  forming  a  dense  stratum  at  the  bottom  of  the  vessel ;  but  on 
continuing  the  passage  of  the  gas  this  becomes  pasty  from  deposition 
of  crystals  of  the  bicarbonate.  The  alcohol  containing  chlorides  and 
nitrates  is  now  decanted  and  replaced  by  a  fresh  quantity,  the  pas- 
sage of  the  gas  being  continued,  with  occasional  agitation,  until  the 
pasty  precipitate  becomes  pulverulent  and  the  liquid  is  saturated 
with  carbonic  anhydride.  The  bicarbonate,  after  being  thoroughly 
washed  with  alcohol,  is  found  to  be  pure. 


PHARMACEUTICAL    CHEMISTRY.  109 

A  New  Test  for  Alcohol.  E.  W.  Davy.  (Proc.  Eoyal  Irish 
Academy,  ii.,  570.)  The  reagent  recommended  is  a  solution  of  1 
part  of  molybdic  acid  in  10  parts  of  pure  concentrated  sulphuric 
acid.  On  warming'  this  solution  gently  in  a  porcelain  dish,  and  then 
adding  a  few  drops  of  a  liquid  containing  alcohol,  a  blue  coloration 
is  developed,  which  gradually  disappears  on  exposure  to  the  air,  but 
is  reproduced  on  expelling  the  absorbed  naoisture  by  evaporation. 
The  alcohol  may  thus  be  detected  in  a  single  drop  of  a  mixture 
containing  1  part  of  alcohol  to  1000  parts  of  water.  The  test  is 
specially  recommended  for  the  detection  of  alcohol  in  chloroform 
and  chloral  hydrate. 

Shellac  and  Sarcosinic  Acid,  J.  Hertz.  {Arcliiv  der  Fharmacie 
[3],  viii.,  234;  Journal  Ghein.  6'oc.,  April,  1877.)  This  vaz^iety  of 
shellac  was  obtained  from  Mexico,  where  it  is  known  as  "  somo  de 
sonora,"  and  called  by  the  Indians  "arre."  It  exudes  from  the 
Mimosa  coccifera,  the  native  name  for  which  is  "  tzinacaia  cuit- 
laquahuitl."  It  has  an  astringent,  bitter  taste,  and  a  yellowish  or 
brownish  colour.  It  is  used  as  a  remedy  for  diarrhoea  and  uterine 
discharges. 

East  Indian  shellacs  ai'e  treated  with  water  before  they  ai'e  de- 
livered to  the  European  market,  to  extract  an  acid  substance  and  a 
red  dye,  which  forms  10  per  cent,  of  the  weight  of  the  crude  gum. 

The  American  specimen  lost  6  per  cent,  of  its  weight  on  treatment 
with  hot  water.  It  was  then  treated  with  alcohol,  which  dissolved 
about  half;  the  solution,  on  evaporation,  left  a  transparent  brittle 
residue,  which  had  all  the  appearance  of  good  shellac.  The  portion 
which  refused  to  dissolve  in  alcohol  was  soluble  in  boiling  potash, 
with  a  fine  red  colour ;  on  addition  of  acid  the  solution  became 
colourless,  and  a  yellowish  white  resin  separated,  which  was  partially 
soluble  in  alcohol.    These  reactions  correspond  with  those  of  shellac. 

The  aqueous  solution  contained  two  substances, — a  colourino- 
matter  and  an  acid  body.  The  colouring  matter  was  removed  by 
lead  acetate,  and  the  filtrate  evaporated  after  removal  of  the  lead. 
The  colouring  matter  was  soluble  in  water  with  a  fine  red  colour, 
and  insoluble  in  alcohol  and  in  ether.  It  could  not  be  obtained  in  a 
crystalline  state.  Its  solution  showed  a  strongly  acid  reaction. 
The  filtrate  from  the  colouring  matter  deposited  crystals,  easily 
soluble  in  water  and  insoluble  in  alcohol  and  in  ether.  They 
were  purified  by  solution  in  boiling  aqueous  alcohol,  from  which 
they  deposited  as  a  powder  on  cooling.  The  formula  of  the  acid 
was  found  to  be  Cg  H^  N  Oo,  and  it  was  named  "  sarcosinic  acid." 

The  hariikm  salt  is  an  amorphous  powder,  soluble  in  water  but 


no  YEAU-BOOK    OF    mARMACY. 

Dot  in  alcohol.  The  silccj'  salt,  C^HgNOoAq,  forms  yellowish 
white  nodules,  and  is  reduced  on  exposure  to  light.  The  sodiuni 
salt  crystallizes  with  G  molecules  of  water,  and  forms  colourless 
hexagonal  tables.  The  calcium  salt  crystallizes  with  one  molecule 
of  water,  and  is  an  amorphous  powder. 

The  acid  does  not  evolv^e  ammonia  when  boiled  with  caustic 
soda,  but  on  heating  with  soda-lime  it  does.  It  melts  at  195°,  and 
chars  at  a  higher  temperatui-e  without  subliming.  The  acid  is 
isomeric  with  alanine,  sarcosine,  lactamide,  and  urethane.  The 
two  latter,  however,  are  indifferent  bodies  :  lactamide,  when  heated 
with  soda,  decomposes  into  lactic  acid  and  ammonia ;  urethane  into 
carbonic  anhydride,  ammonia,  and  ethyl  alcohol.  Sarcosine  unites 
only  with  acid,  and  it  is  doubtful  whether  it  is  an  amido-acid ;  ifc 
evolves  methylamiuc  on  ignition  with  soda-lime.  Alanine,  when 
treated  with  nitrous  anhydride,  yields  lactic  acid.  These  bodies 
are  assumed,  therefore,  to  have  the  following  constitution  : — 


Urethane.  Lactamide.  Sarcosine.  Alanine. 

CO.NH.,  ^CHoOH  CHo.NH(CHa)  ^CH.,.NH., 

1  ■  CH,<"  I     '  I     "  CH,<'   I 

CO.OC.H-,  ^CO.NH,  CO.OH  ^C  0. 0  H 


Sarcosinic  acid  appears  to  be  move  nearly  related  to  sarcosine 
and  alanine  than  to  lactamide  or  urethane;  yet  sarcosine  is  a  base, 
while  sarcosinic  acid  is  a  true  acid.  The  acid,  however,  was  found 
to  form  a  hydrochlorate  and  nitrate.  With  nitrous  anhydride  nitro- 
gen was  evolved  and  lactic  acid  w-as  formed.  The  acid,  therefore, 
has  great  analogy  to  lactic  acid,  from  which  it  differs  only  in 
taste,  crystalline  form,  and  marked  acid  properties.  The  author 
attributes  to  it  the  same  constitutional  formula  as  to  alanine;  bub 
intends  to  attempt  to  prepare  it  synthetically,  to  decide  wherein 
the  difference  lies.  E.  Reichart  attributes  to  it  the  formula, 
C  Ho.  X  Ho.  C  Ho.  C  0  0  H. 

Note  on  Litmus.  H.  "W.  Mitchell.  {American  Chemist;  from 
a  paper  read  before  tlie  American  Chemical  Society,  June,  1876.) 
Wartha  has  separated  four  organic  bodies  from  litmus.  The 
first  is  obtained  by  treating  commercial  litmus  with  alcohol  of  about 
90  per  cent.,  filtering  cold,  and  boiling  the  clear  tincture ;  where- 
upon indigo  is  precipitated  as  a  fine  power,  according  to  the  author. 
The  second  body  is  obtained  by  evaporating  the  violet  red  mother- 
liquor  ;  it  is  a  beautiful  red,  or,  from  many  varieties,  green  fluor- 
escent substance,  indifferent  to  acids.  The  litmus  residue  left  after 
treatment  with  alcohol  is  digested  with  distilled  water  for  twenty- 
four  hours ;  after  which  the  deep  coloured  solution  is  evaporated  on 


PHARMACEUTICAL    CHEMISTRY.  Ill 

the  water  bath,  and  the  residuary  extract  is  treated  several  times 
"with  absolate  alcohol  containing  a  little  glacial  acetic  acid,  and  again 
evaporated,  until  it  forms  a  brown  powdery  mass.  This  mass  is 
now  exhausted  with  absolute  alcohol  and  acetic  acid,  whereby 
a  largo  quantity  of  a  scarlet  red  body  is  dissolved,  which  resembles 
orcin,  and  becomes  purple  red  in  place  of  blue  with  ammonia. 
The  portion  of  the  brown  powder  insoluble  in  the  acidified 
alcoholic  solution  consists  of  litmus  colouring  matter  in  a  very 
pure  form ;  so  pure,  in  fact,  that  by  means  of  it  the  carbonated 
alkaline  earths  contained  in  spring  waters  may  be  titrated  with  as 
great  delicacy  as  by  the  use  of  cochineal  mixture ;  which  is  far 
from  being  the  case  with  crude  litmus.  To  get  this  substance 
perfectly  pure,  it  is  first  washed  with  absolute  alcohol,  then  dis- 
solved in  a  small  quantity  of  water  and  thrown  into  a  large  excess 
of  alcohol  and  the  flocculent  purple  precipitate  is  collected  and  ao-aia 
thoroughly  washed  with  alcohol.  In  repeating  the  above  experi- 
ments, the  author  confirms  Wartha's  results  in  every  particular 
save  as  regards  the  indigo,  Avhich  could  not  be  obtained  by  boilino- 
the  alcoholic  tincture.  The  fluorescent  body  above  mentioned  is 
violet  or  purple,  and  gives  a  solution  in  alcohol  of  a  similar 
colour,  which  shows  a  beautiful  green  fluorescence  with  sunlight, 
and  with  the  spectroscope  gives  a  very  characteristic  absorption- 
band  in  the  green,  together  with  an  almost  total  absorption  of  the 
violet  end  of  the  spectrum.  It  is  soluble  in  water,  amylic  alcohol, 
and  common  ether;  very  soluble  in  alcohol;  but  is  insoluble  in  carbon 
bisulphide,  chloroform,  petroleum  naphtha,  and  turpentine.  The 
solutions,  both  in  amylic  alcohol  and  in  ether,  exhibit  a  beautiful 
fluorescence ;  but  the  ethex-eal  solution  shows  the  absorption-band 
in  the  green  only  very  faintly.  The  body  which  resembles  orcin 
shows  a  very  faint  fluorescence ;  its  alcoholic  solution  gives  a 
spectrum  in  which  the  absorption  is  characteristic  and  quite  dis- 
tinct from  that  of  the  last.  It  is  slightly  soluble  in  water,  veiy 
soluble  in  alcohol,  but  seems  to  be  insoluble  in  ether,  chloroform, 
carbon  disulphide,  and  petroleum  naphtha.  The  pure  litmus  col- 
ouring matter  is  insoluble  in  alcohol,  ether,  chloroform,  bisulphide, 
of  carbon,  and  petroleum  najjhtha ;  very  soluble  in  water.  It  turns 
blue  with  ammonia,  and  yields  with  alkaline  solutions  a  beautiful 
violet  lake  with  alumina,  one  of  a  pale  violet  colour  with  stannous 
acetate,  and  deep  blue  lakes  with  calcium  and  barium. 

The  residue  left  after  extracting  the  pure  litmus  dissolves  to 
some  extent  in  hydrochloric  acid.  The  residue  insoluble  in  hydro- 
chloric acid  consists  mostly  of  fine  sand,  but  yields  some  colouring 


112  YEAK-BOOK    OF    PHARMACY. 

matter  to  strong  ammoiiic  hydrate.  About  25  grams  of  the  pure 
colouriug  matter  (15  grams  of  the  body  like  orcin,  and  10  grams  of 
the  fluorescent  body)  wore  obtained  per  ounce  of  litmus. 

Emodin  from  Rhamnus  Frangulae  Bark.  C.  Liebermann  and 
M.  Waldstein.  (^Ber.  der  deutscli.  Ghem.-Ges.,  1870,  1775-1778.) 
Old  frangula  bark  was  exhausted  with  dilute  soda  solution,  and 
the  liquid  precipitated  by  hydrochloric  acid  ;  the  precipitate  was 
again  boiled  with  soda,  and  precipitated  by  H  CI;  then  washed,  dried, 
and  repeatedly  crystallized  from  boiling  absolute  alcohol.  A  small 
quantity  of  a  glucoside  was  removed  by  boiling  with  dilute  sul- 
phuric acid  and  crystallizing  fi'om  alcohol  or  glacial  acetic  acid. 
The  authors  obtained  it  from  the  latter  liquid  in  the  form  of  orange 
coloured  silky  needles,  containing  acetic  acid  and  water,  which  are 
expelled  at  140°  C,  the  crystals  becoming  opaque. 

Ultimate  analysis  proving  the  composition  of  the  crystals  to  be 
Ci5  HjQ  O5,  their  identity  with  emodin  from  rhubarb  was  further 
proved  by  the  solubilities,  form  of  crystals,  and  colour  of  alkaline 
solution  ;  also  by  the  following  behaviour  : — baryta  and  lime  water 
yielded  red  precipitates,  which  were  soluble  in  boiling  water  with  a 
red  colour  ;  alum  solution  dissolved  slightly  with  a  yellow  colour, 
ammonia  yielding  red  precipitates ;  evaporation  with  nitric  acid 
yielded  yellow  nitro  compounds,  soluble  in  water  with  a  red  colour. 
The  behaviour  towards  glacial  acetic  acid  was  that  stated  above. 

The  frangulinic  acid  of  Faust  differs  in  some  respects  from  emodin; 
it  is  not  impossible  that  it  may  be  contained  in  the  recent  bark,  and 
gradually  converted  into  emodin  by  oxidation. 

Preparation  of  Pure  Bismuth  and  Bismuth  Compounds.  H. 
Thiirach.  (Journ.  praht.  Chem.  [2],  xiv.,  oO'J-olG  ;  Juuru.  Chem. 
Soc,  March,  1877,  283.)  The  usual  impurities,  even  in  what  is 
sold  as  pui-e  bismuth,  are  silver  and  iron.  Quesneville's  process, 
viz.,  fusing  the  metal  with  niti'e,  has  the  disadvantage  of  being  ex- 
tremely wasteful,  a  large  quantity  of  bismuth  being  oxidised.  !Nor 
can  bismuth  be  separated  from  it  by  precipitation  as  oxychloride 
with  water,  for  iron  is  invariably  a  constituent  of  the  precipitate. 
If  the  bismuth  be  fused  under  a  mixture  of  potassium  chlorate  and 
a  little  sodium  carbonate,  the  iron  is  completely  oxidised,  while  very 
little  bismuth  is  lost ;  for  the  fused  mass  does  not  become  alkaline, 
as  is  the  case  when  nitre  is  used  as  a  flux.  Two  to  five  per  cent,  of 
sodium  carbonate  should  be  added,  and  the  fusion  should  last  for 
a  quarter  of  an  hour.  No  method  of  separating  bismuth  from  iron 
by  the  wet  method  was  successful,  excef^t  by  crystallizing  the  double 
chloride  of  bismuth  and  the  alkalies,  and  by  precipitating  the  bismuth 


PHARMACEUTICAL    CHEMISTRY.  113 

from  a  sliglitly  acid  solution  with  oxalic  acid.  The  bismuth  oxalate, 
Big  (Co  0^  )3  +  15  Ho  0,  comes  down  absolutely  free  from  iron.  Too 
large  an  excess  of  oxalic  acid  should  be  avoided,  for  the  oxalate  is 
slightly  soluble  in  the  acid  ;  the  precipitate  should  not  be  allowed  to 
stand  too  long  in  contact  with  water,  else  the  basic  oxide  is  formed 
which  retains  the  iron.  The  oxalate  on  ignition  yields  metallic 
bismuth. 

This  process  has  not  been  attempted  quantitatively. 

The  only  method  of  separating  silver  from  bismuth  is  to  oxidise 
the  bismuth,  and  leave  metallic  silver. 

Bismuth  is  best  pi'ecipitated  as  sulphide.  The  liquid  is  then 
warmed,  when  the  sulphide  cakes  together  and  may  be  easily  filtered 
and  washed.  On  ignition  in  air  it  is  converted  into  bismuth  oxide, 
and  may  be  weighed  as  such. 

Santonin  and  Santonic  Acid.  MM.  Cannizzaro  and  Sestini. 
(L^Union  Pharmaceutique,  xvii.,  136.)  Santonic  acid  is  obtained 
from  santonin  by  boiling  the  latter  for  twelve  hours  with  a  satu- 
rated solution  of  barium  hydrate,  decomposing  the  barium  santonate 
thus  formed  with  hydrochloric  acid,  and  taking  up  the  liberated 
santonic  acid  by  ether.  The  authors  have  previously  shown  (1873) 
that  this  substance  is  isomeric  with  santoninic  acid,  but  not  resolv- 
able like  the  latter  into  santonin  and  water. 

Pure  santonic  acid  forms  orthorhombic  prisms  which,  unlike 
satonin,  are  not  affected  by  light  and  do  not  produce  a  violet  color- 
ation with  potassium  hydrate.  Its  composition  is  represented  by  the 
formula  C;^5  Hog  O^  ;  it  fuses  at  161°-163°  C,  and  is  readily  soluble 
in  boiling  water,  alcohol,  ether,  and  chloroform.  Its  sodium  and 
barium  salts — Na  Ci5H^9  04,  and  Ba 2  0^5  H^gO^ — are  extremely  so- 
luble in  water  and  difficult  to  crystallize.  Though  the  authors  have 
hitherto  been  unable  to  convert  santonic  acid  into  santonin,  they 
have  produced  from  it  metasantonin,  a  substance  isomeric  with  san- 
tonin, by  boiling  it  with  hydriodic  acid  and  phosphorus.  This  new 
derivative  forms  white  crystals,  which  fail  to  yield  a  santonate  on 
boiling  with  solution  of  barium  hydrate,  and  which  can  be  distilled 
in  a  vacuum  without  suffering  decomposition. 

By  the  action  of  bromine  on  an  acetic  acid  solution  of  santonin, 
the  authors  obtained  a  body  crystallizing  in  red  needles  and  corres- 
ponding to  the  formula  Cjj  Hjg  O.5  Br,. 

Testing  of  Salicylic  Acid.  H.  Kolbe.  (Journ.  lorald.  Chem.  [2], 
xiv.,  143).  Half  a  gram  of  the  acid  to  be  tested  is  dissolved  in 
about  five  grams  of  strong  alcohol,  and  the  clear  liquid  allowed 
to  evaporate  slowly  in  a  watch  glass  at  the  ordinary  temperature. 


114  YEAR-BOOK   OF   PHARMACY. 

Tiie  acid  will  form  groups  of  fine  efflorescent  crystals  round  the 
edge  of  the  glass.  These  crystals  should  be  of  a  pure  white  colour, 
if  the  acid  was  previously  crystalline  ;  but  more  or  less  yellow  if 
precipitated.     If  the  crystals  are  at  all  brown,  the  acid  is  impure. 

Simplified  Method  of  Extracting  Poisonous  Alkaloids  in  Forensic 
Investigations.  F.  Selmi.  (Journ.  Chem.  Soc,  from  Gaz.  Gkim. 
ItaL,  vi.,  15o.)  The  alcoholic  extract  of  the  viscera,  acidified  and 
filtered,  is  evaporated  at  G5°,  the  residue  taken  up  with  water,  filtered 
to  separate  fatty  matters,  and  decolorised  by  means  of  basic  acetate 
of  lead,  leaving  the  solution  in  contact  with  the  air  for  24  hours.  It 
is  then  filtered,  the  lead  precipitated  with  sulphuretted  hydrogen, 
and  the  solution,  after  concentration,  repeatedly  extracted  with 
ether.  The  ethereal  solution  is  then  saturated  with  dry  cai'bonic 
anhydride,  which  generally  causes  a  precipitate  of  minute  drops, 
adhering  to  the  sides  of  the  vessel,  and  containing  some  of  the 
alkaloids.  The  ethereal  solution  is  then  poured  into  a  clean  vessel, 
mixed  with  about  half  its  volume  of  water,  and  a  current  of  carbonic 
anhydride  passed  for  20  minutes,  which  may  cause  the  precipitation 
of  other  alkaloids  not  precipitated  by  dry  carbonic  anhydi'ide. 
Usually  the  whole  of  the  alkaloids  present  in  the  ether  are  thrown 
duwn  by  these  means  ;  but  if  not,  the  solution  is  dehydrated  by 
agitation  with  barium  oxide,  asid  then  a  solution  of  tartaric  acid  in 
ether  added  to  the  clear  liquid,  taking  great  care  not  to  employ 
excess  of  acid.  This  throws  down  any  alkaloid  that  may  remain. 
In  order  to  extract  any  alkaloids  that  may  still  remain  in  the  viscera, 
they  are  mixed  with  barium  hydrate  and  a  little  water,  and  then 
agitated  with  purified  amylic  alcohol  ;  the  alkaloids  may  subse- 
quently be  extracted  from  the  alcohol  by  agitation  with  very  dilute 
sulphuric  acid. 

Notes  on  Atropine.  F.  Selmi.  (Gazzetfa  Chimica  Italkma, 
vi.,  l'J-5.)  In  connection  with  the  foregoing  article  on  the  extraction 
of  poisonous  alkaloids,  the  author  refers  specially  to  atropine  and 
some  of  its  decompo.«ition  products.  As  atropine  is  readily  decom- 
jjosed  into  tropine  and  atro})ic  acid,  and  might  become  altered  in  the 
process  of  extraction  from  the  viscera,  etc.,  he  studied  the  action  of 
various  reagents  on  the  alkaloid.  Boiled  with  a  solution  of  barium 
hydrate  in  contact  with  the  air,  it  gave  a  pleasant  odour  of  haw- 
thorn flowers,  but  no  odour  was  observed  on  distilling  the  mixture. 
The  residue  contained  troinne,  which  was  extracted  with  ether. 
Atropine  was  decomposed  when  boiled  with  dilute  sulphuric  acid, 
or  with  a  solution  of  tartaric  acid,  but  no  odour  was  developed ;  a 
substance  (a)  being  obtained  from  the  solution  on  treatment  with 


PHARMACEUTICAL    CHEMISTRY. 


li: 


ether,  very  different  in  its  reactions  from  tropine.  The  action  of 
ammonia  on  atropine  yields  two  substances  of  the  nature  of  an  alka- 
loid ;  one  (b)  precipitable  by  carbonic  anhydride  from  the  ethereal 
solution  ;  the  other  (c)  not  precipitable.  Their  reactions  are  as 
follows  : — 


Tropine. 

A. 

B. 

C. 

Tannic  Acid     .... 

White 

White 

White 

Iodized  Hydriodic  Acid    . 

Brown  drops 

— 

Brown 

Brown 

Platinum  Perchloride 

Turbidity 

None 

None 

None 

Picric  Acid       .... 

— 

Id. 

Id. 

Id. 

Meyer's  Keagent 

^Vhite 

Id. 

Id. 

Id. 

Gold  Chloride  .... 

Yellow 

YeUow 

Yellow 

YeUow 

Brominated  Hydrobromic  Acid 

None 

— 

Yellowish 

Id. 

Mercuric  Chloride    . 

Straw  yellow 

White 

White 

White 

Sodium  Phosphotungstate 

— 

Id. 

Id. 

Iodide  of  Potassium  and  Bis- 

muth     

— 

Orange  yeU. 

Yellow 

Yellow 

Iodide  of  Potassium  and  Cad- 

mium   

White 

— 

White 

White 

From  experiments  made  on  the  putrefied  viscera  of  an  animal 
poisoned  -with  atropine,  and  on  the  alkaloids  generated  by  the  putre- 
factive process  in  the  viscera  themselves,  the  author  finds  that  one 
of  those  formed  in  the  latter  case,  and  which  may  be  extracted  by 
the  use  of  amylic  alcohol  (although  not  by  ether),  closely  resembles 
atropine  in  its  action  on  the  animal  organism.  Atropine  may  be 
distinctly  recognised,  however,  by  the  characteristic  odour  of  haw- 
thorn given  off  during  evaporation  with  baryta  and  by  the  bitter 
taste  and  poisonous  action  of  the  ethereal  extract,  accompanied  by 
dilation  of  the  pupil. 

Estimation  of  Urea,  M.  Depaire.  (Joiirn.  de  Pharm.  d'Anvers, 
February,  1877.)  The  author  desired  to  arrive  at  a  process  which 
would  give  reliable  results,  even  in  the  hands  of  those  persons  who  are 
not  specially  trained  in  chemical  manipulations.  He  adopts  the  pro- 
cess of  Yvon  and  Esbach,  with  certain  modifications.  Sodium  hypo- 
bromite  is  used  with  excess  of  an  alkali,  to  decompose  the  urea,  and 
the  resulting  nitrogen  gas  is  measured  over  water,  which  retains 
the  other  products  of  the  decomposition,  namely,  carbonic  anhy- 
dride and  water.  10  centigrams  of  urea,  decomposed  by  sodium 
hypobromite  in  alkaline  solution,  gives  off  a  volume  of  nitrogen 
which  measures  37  c.c.  at  0°  C,  and  760  mm.  pressure.  In  order 
to  avoid  calculations,  the  plan  of  Yvon  may  be  adopted,  namely 
to  make  a  preliminary  trial  upon  a  known  solution  of  urea  just 
before   examining    the   urine,    and    to    compare   the    two   results. 


116  YEAR-BOOK    OF    PHARMACY. 

Naturally  the  amount  of  urea  corresponding  to  the  urine  must  be 
increased  in  the  same  ratio  as  the  figure  found  for  010  gram  of 
pure  urea  exceeds  37.  Supposing  10  centigrams  of  pui-e  urea 
have  been  treated  in  the  manner  described,  and  have  disengaged  40 
c.c.  of  nitrogen  and  10  c.c.  of  an  unknown  solution  of  urea,  or  of 
urine,  disengage  under  the  same  circumstances  (iG  c.c.  The  quantity 
of  urea  contained  in  the  latter  will  be  found  as  follows  : — 40  :  10  = 
66  :.T  :a'  =  16'5  centigrams.  The  result  will  be  correct  as  long  as 
there  is  not  present  an  excess  of  uric  acid  or  albumen.  In  the 
former  case,  it  is  best  to  expose  the  urine  to  cold,  to  promote  the 
crystallization  of  the  uric  acid  and  urates,  which  are  then  removed  ; 
and  in  the  latter  case,  the  urine  must  be  heated  in  a  closed  vessel, 
so  as  to  coagulate  the  albumen. 

Titration  of  Oxalic  Acid  and  Oxalates.  F.  Jean  and  H.  Pellet. 
(Bidl.  de  la  Soc.  Chim.;  Chem.  Netvs,  35,  248.)  The  determination 
of  free  oxalic  acid,  or  of  oxalates,  may  be  effected  very  exactly  by 
the  aid  of  baryta  water  and  a  standard  solution  of  sulphuric  acid. 
For  this  purpose  the  solution  to  be  assayed  is  carefully  neutralized 
with  a  dilute  solution  of  soda,  then  mixed  with  baryta  water  in  a 
slight  excess  and  filtered.  The  filtrate  is  then  mixed  with  seltzer 
water,  raised  to  the  boiling  point,  separated  by  filtration  from  the 
carbonate  of  baryta,  and  in  the  clear  liquid  the  alkali  is  titrated 
with  standard  sulphuric  acid.  00777  gram  of  S  O3  H  0  =  O'l  gram 
C2O33HO.  10  c.c.  of  a  solution  containing  1  per  cent,  of  C^OaSHO, 
required  11 '8  c.c.  of  a  standard  acid,  of  which  10  c.c.  =  0"066  gram  of 
SO3HO;  that  is,  00778  of  sulphuric  acid.  O'lOOOl  gram  of  oxalic 
acid  was  thus  found,  instead  of  01  gram.  In  another  assay  the  num- 
ber obtained  was  0"0999  gram. 

In  order  that  this  process  of  titration  may  give  good  results,  care 
must  be  taken  to  separate  the  oxalate  of  baryta  before  adding  seltzer 
water ;  for  this  salt  is  very  sensibly  decomposed  by  carbonic  acid, 
and  the  neglect  of  this  precaution  would  lead  to  grave  errors. 
The  authors  also  applied  this  process  to  the  titration  of  borates  and 
tartrates  ;  but  the  assays  made  with  this  view  never  gave  good 
results.  With  boric  acid  it  is  impossible  to  seize  the  point  of  neutra- 
lization ;  and  the  borates  of  baryta  are  all  more  or  less  soluble  in  an 
alkaline  liquid.  The  tartrate  of  baryta  is  equally  soluble  in  baryta 
water  and  in  alkalies,  in  the  latter  case  forming  double  tarti-ates. 

Titration  of  Chlorides  in  the  Presence  of  Phosphates.  H.  Pel- 
let. {Bull.  Soc.  Chim.  [2],  xxii.,  246.)  The  solution  to  be  tested 
is  acidified  with  nitric  acid,  and  then  neutralized  with  calcium  car- 
bonate.    The   chlorine  may  now  be  titrated   with  silver  nitrate  in 


PHARMACEUTICAL    CHEMISTRY.  117 

the  usual  way,  potassium  chromate  being  used  as  an  indicator.  A 
correction  should  be  made  for  the  excess  of  silver  nitrate  by  mixing 
a  quantity  of  distilled  water,  equal  in  volume  to  that  of  the  liquid 
in  which  the  chlorine  was  determined,  with  a  few  drops  of  solution  of 
potassium  chromate,  and  adding  the  standard  silver  solution  till  the 
red  coloration  is  produced.  The  presence  of  sugar,  or  similar  or- 
ganic substances,  does  not  interfere  with  the  process. 

Indirect  Estimation  of  Ammonia  in  Ammonium  Salts.  H.  Pel- 
let. (Bidl.  Soc.  Chim.  [2],  xxii.,  250.)  A  solution  of  10  grams 
of  the  ammonium  salt  in  30  or  40  c.c.  of  water  is  mixed  with  a  few 
decigrams  of  pure  calcium  carbonate,  to  insure  perfect  neutrality. 
It  is  then  made  up  to  500  c.c  ,  and  filtered.  The  filtrate  is  now 
boiled  with  an  excess  of  titrated  solution  of  sodium  hydrate  until 
the  ammonia  is  completely  expelled,  when  the  excess  of  soda  is 
determined  with  titrated  sulphuric  acid. 

Chemical  Constitution  of  Chlorinated  Lime.  C.  Stahlschmidt. 
{Bimjl.  pohjt.  Joitrn.,  ccxxi.,  335-3-15 ;  Jouni.  Chem.  Soc,  March, 
1877.)  G-ay-Lussac  represented  chloride  of  lime  by  the  formula 
Ca  0  C1.2,  according  to  which  pure  chloride  of  lime  should  contain 
no  calcium  chloride.  Gopner  sought  to  establish  this  view  by  the 
assumption  that  chloride  of  lime,  on  treatment  with  dilute  mineral 
acids,  yields  pure  chlorine,  and  no  hypochlorous  acid.  This  assump- 
tion has  been  proved  untenable  by  Schorlemmer,  who  obtained  hypo- 
chlorous  acid  by  distilling  with  dilute  nitric  acid.  Richter  and  Junker 
also  contended  that  no  calcium  chloride  is  contained  in  chloride  of 
lime ;  and  this  they  sought  to  prove  by  boiling  a  solution  of  1  gram 
of  chloride  of  lime  in  20  c.c.  of  a  20  per  cent,  phosphoric  acid  solution, 
till  all  smell  of  chlorine  had  disappeared,  and  then  find  no  calcium 
chloride  left.  Thus  they  assumed  that  such  a  phosphoric  acid  solu- 
tion cannot  decompose  calcium  chloride  on  being  boiled  with  it,  and 
that  only  the  chlorine  of  the  compound  Ca  0.  CL  is  liberated.  The 
author  has,  however,  found  that  phosphoric  acid  solutions  will 
decompose  calcium  chloride  with  liberation  of  hydrochloric  acid. 
Kolb  found  that  the  richest  chloride  of  lime  he  could  prepare  con- 
tained 88'72  per  cent,  actual  chlorine  ;  and  this  coincides  with  a 
formula,  3 (Ca 0.  K, 0)  +  4 CI,  or  2  (Ca  0. H,  0.  CI.)  +  Ca  O.  H.  0.  This 
chloride  of  lime  should  be  decomposed  by  water,  as  follows  : — 
3  (Ca  0.  H„  0)  +  4  CI  =  Ca  0  H.,  0  as  a  precipitate,  and  2  Ca  0  CI^ 
going  into  solution.  Then  the  true  constitution  of  the  chloride  of 
lime  dissolved  in  water,  as  given  by  Ballard,  should  be  :  2  Ca  0  CI. 
=  Ca  0  CI.,  0  +  Ca  C\,. 

In  a  more  recent  publication,  Kolb  gives  to  chloride  of  lime  this 


118  YEAR-BOOK   OF    PHARMACY. 

formula,  2  (Ca  0  Clo)  +  Ca  0  +  3  H,  0  ;  the  filtered  solution  consisted 
as  before  of  Ca  0.  CL  0  and  Ca  CL.  In  the  first  formula,  Kolbassnmes 
that  water  belongs  to  the  constitution  of  chloride  of  lime;  but  after- 
wards he  appears  to  forsake  this  view.    According  to  Kolb  also,  three 
molecnles  of  calcium  hydrate  are  acted  on  by  four  atoms  of  chlorine 
to  form  chloride  of  lime;  and  thus  far  he  and  the  author  are  agreed. 
The  author  used  in  his  experiments  only  chloride  of  lime  which 
contained  39  per  cent,  of  actual  chlorine,  and  which  had  been  formed 
exactly  according  to  the  formula  3  Ca  H.>  0..  +  4  CI.     In  a  beaker  a 
quantity  of  the  above  chloride  of  lime  was  treated  with  water,  a 
trace  of  cobalt  sulphate  added,   and  the  whole  boiled.  In  this  man- 
ner the  calcium  hypochlorite  formed  is  converted,  -with  liberation  of 
oxygen,  into  calcium  chlorate  and  calcium  chloride,  without  a  trace  of 
clilorine  escaping.    The  boiling  was  continued  till  a  di'op  of  the  solu- 
tion produced  no  coloration  on  iodized  starch  paper.     Carbonic  acid 
was  then  passed  into  the  solution  for  several  hours,  whereby  the  cal- 
cium hydrate  separated  at  first  was  converted  into  calcium  carbonate. 
Finally,  the  whole  was  boiled  for  some  time  to  drive  off"  free  carbonic 
acid,  and  separate  any  carbonate  that  might  have  been  dissolved 
thereby.      The  precipitate  was   collected  on  a   filter,   washed   and 
weighed,  and  the  amount  of  caustic  lime  therein  calculated.     This 
amount  agreed  well  with  the  equation, — 

2  CaHClO,  +  CaCla  +  2  H.O  =  Ca  Cl^  0^  +  Ca  H^  0^  +  Ca  CI,  +  2  H^  0. 

The  chloride  of  lime  was  next  treated  with  freshly  prepared  sul- 
phurous acid — quite  free  from  sulphuric  acid — until  the  reaction  with 
iodized  paper  ceased.  Thus  two  molecules  of  sulphurous  acid  were 
converted  into  sulphuric  acid  by  one  molecule  of  hypochlorous  acid, 
and  this  united  with  an  equivalent  quantity  of  lime,  setting  free  a 
corresponding  proportion  of  hydrochloric  acid.  The  whole  was  then 
evaporated  on  the  water  bath  to  dryness,  when  the  free  hydrochloric 
acid  escaped,  and  sulphate  of  lime  remained,  together  with  one  mole- 
cule of  calcium  chloride  originally  existing  in  the  dry  chloride  of 
1  ime : — 

Ca  CI2  O2  +  Ca  H2  O2  +  Ca  CL  +  2  S  O2  =  2  Ca  S  O4  +  2  H  CI  +  Ca  CI . 

The  calcium  chloride  was  then  estimated  with  silver  solution. 
The  results  agreed  well  with  the  formula  quoted. 

The  behaviour  of  chloride  of  lime  at  high  temperatures  was  next 
tested.  It  is  already  known  that  chloi'ide  of  lime,  under  the 
influence  of  heat,  decomposes  with  formation  of  calcium  chloride 
and  chlorate,  and  liberation  of  oxygen  gas  and  sometimes  of  chlorine. 


PHARMACEUTICAL   CHEMISTRY.  119 

With  a  less  intense  heat,  according  to  Morin,  one-third  of  the  cal- 
cium hypochlorite  passes  into  chloride  and  chlorate,  whilst  two- 
thirds  remain  unaltered  ;  and  then  a  stronger  heat  decomposes  this 
into  calcium  chloride  and  oxygen. 

When  freshly  prepared  chloride  of  lime  is  heated  in  a  bulb  tube 
between  100°  and  120°,  water  and  chlorine  escape.  When  the  tem- 
perature rises,  no  more  chlorine  escapes  after  a  certain  point ;  but 
at  and  above  300°,  pure  oxygen  is  liberated.  When  an  incipient  red 
heat  is  attained,  the  whole  melts  to  a  fluid  mass,  clear  and  trans- 
parent as  water,  resembling  fused  nitre  ;  and  on  cooling  solidifles  to 
a  crystalline  mass,  resembling  the  latter  salt  in  appearance  under  like 
conditions.  At  a  red  heat  a  further  liberation  of  gas  takes  place,  and 
the  mass  then  becomes  muddy,  opaque,  and  thick,  with  separation  of 
an  insoluble  compound.  By  heating  chloride  of  lime,  all  the  chlorine 
which  escapes  does  so  as  chlorine,  not  a  trace  as  hydrochloric  acid. 

For  the  estimation  of  the  water  in  chloride  of  lime,  a  portion  of 
the  body  was  heated  in  a  bulb  tube,  first  slowly,  and  then  after- 
wards to  ignition  ;  a  current  of  dry  air,  free  from  carbon  dioxide, 
being  passed  over  it,  and  the  water  escaping  being  retained  by  a 
calcium  chloride  tube. 

The  amount  of  water  thus  estimated  agreed  very  well  with  the 
formula,  2  Ca  CI  H  Oo  +  Ca  CI.  +  2  Ho  0.  It  appears  then  that  this 
final  molecule  of  water  is  not  liberated  even  at  a  red  heat. 

Another  portion  of  the  chloride  of  lime  was  now  mixed  with  dry, 
ignited  sodium  carbonate,  and  the  whole  ignited  in  the  bulb  tube, 
so  that  the  mass  does  not  quite  fuse.  Three  molecules  of  water  were 
thus  set  free,  with  simultaneous  formation  of  calcium  carbonate, 
sodium  chloride,  and  free  oxygen.  The  numbers  obtained  com- 
pletely bear  out  the  formula  2  Ca  H  CI  0,  +  Ca  CI,  +  2  H.  0. 

By  the  first  heating  9"96  per  cent,  of  water  escaped,  and  by  the 
second  5'04  per  cent. ;  total,  15  per  cent. 

li;  was  finally  discovered  that  by  heating  chloride  of  lime  to  120°, 
4"6  per  cent,  of  chlorine  were  given  off",  and  by  further  heating  over 
the  lamp  1085  and  ll'GO  per  cent.  Under  these  circumstances  also  , 
9  89  per  cent,  of  water  and  some  oxygen  were  liberated.  At  first  then 
there  are  liberated  from  one  molecule  of  chloride  of  lime,  besides  the 
2  Ho  0,  also  1  CI  +  1  0  ;  and  further,  by  stronger  heating,  |  0  follows. 
The  loss  for  the   2  H_,  0  =    9-89  per  cent.   -^ 

1  CI      =    9-75       „  [  21-03  per  cent. 

10       =    i-3d      „  J 

iO       =    2-19       „ 

Total  loss      -  26-22       „ 


120  YEAR-BOOK   OF    PHARMACY. 

A  portion  of  the  chloride  was  now  ignited,  the  residue  dissolved 
in  water,  and  the  amounts  of  calcium  hydx-ate  and  calcium  chloride 
determined. 

The  results  agreed  sufficiently  well  with  the  formula  mentioned, 
100  parts  of  chloride  of  lime  contain,  according  to  the  formula,  19'23 
per  cent,   of  lime  (Ca  0),  and  53'36  per  cent,  of  calcium  chloride. 

EesriUs  obtained: — Lime,  18"83  and  18"11  percent.  ;  calcium  chlo- 
ride, 51-00  and  52-21<  per  cent. 

It  is  now  shown  that  if  the  actual  compound  in  chloride  of  lime 
were  Ca  0  Clo,  as  according  to  Gopner,  then  by  necessity  it  must 
have  been  formed  as  follows  : — 3  Ca  Ho  Oo  +  4  CI  =  2  Ca  0  CU  + 
Ca  Ho  O2  +  2  Ho  0.  But  this  formula  fails  to  explain  several  of  the 
results  obtained  by  the  author,  and  chiefly  that  by  which  it  appear.s 
that  the  third  molecule  of  water  is  obstinately  retained  in  the  com- 
pound ;  for  had  it  been  contained  as  calcium  hydrate  merely,  the 
strong  heating  would  have  driven  it  forth.  Gdpner's  formula  does 
not  in  any  way  acconnt  for  the  fusibility  of  the  chloride  of  lime  to  a 
clear  glassy  mass  at  a  moderately  high  temperature.  A  mixture  of 
calcium  hydrate,  calcium  chloride,  and  calcium  chlorate  does  not 
possess  this  property.  It  is  considered,  therefore,  that  chloride  of 
lime  contains  no  calcium  hydrate.  Finally,  the  author  considers  it 
as  proved,  that  chloride  of  lime  has  a  constitution  expressed  by  i\^ 
formula,  2  Ca  H  ,C1  Oo  +  Ca  Clg  +  2  Ho  0.  He  also  joins  Frcseuius 
in  the  view  that  the  calcium  chloride  in  this  formula  must  be  con- 
sidered as  standing  outside  the  constitution  of  chloride  of  lime. 

"Whether  the  formula  CaH  CI  Go  or  Ca^^p,  gives      the      true 

situation  of  the  atoms  in  the  compound,  or  whether  this  formula 
should  be  doubled,  the  author  will  not  decide.  He  contents  himself 
with  proving  that  the  bleaching  compound  arises  by  the  replacement 
of  one  atom  of  hydrogen  in  calcium  hydrate  by  an  atom  of  chlorine, 
and  that  the  other  atom  of  hydrogen  remains  in  chemical  combina- 
tion. Finally,  that  the  compound  should  be  regarded  as  a  calcium 
hydro-oxychloride. 

Asparagin  in  Sweet  Almonds.  L.  Fortes.  (Eepert.  dePharm., 
l67*'>,  Oil.)  Having  ol).served  a  peculiar  crystalline  crust  on  the 
outside  of  peeled  almonds  placed  in  absolute  alcohol,  the  author 
made  a  series  of  experiments  to  ascertain  the  nature  of  this  sub- 
stance. It  was  found  to  be  but  little  soluble  in  cold  water;  easily 
soluble  in  hot  water,  hot  dilute  alcohol,  ammonia,  acids  and  acid 
solutions  ;  insoluble  in  strong  alcohol,  ether,  and  fixed  oils.  These 
properties,  together  with  its  composition,  (CjHgNjOg.  Hj  0),  and 


PHARMACEUTICAL    CHEMISTRY.  121 

its  crystallograpliic  character,  prove  the  substance  to  be  aspara- 
gin. 

Volumetric  Estimation  of  Phenol.  "W.  F.  Koppeschaar. 
(Zeitschrift  fur  Analyt.-Chem.,  xv.,  233.)  The  process  generally 
employed  for  the  estimation  of  phenol  in.  the  crude  article  of  com- 
merce is  based  upon  the  fact  that  the  action  of  potassium  hydrate 
on  phenol  results  in  the  formation  of  a  body  soluble  in  water, — 

Ce  H5  0  H  +  K  0  H  -  Cg  Hj  0  K  +  Ho  0. 

The  crude  substance  is  shaken  in  a  graduated  tube  with  a  strong 
solution  of  caustic  potash,  and  the  mixture  allowed  to  stand  until 
the  insoluble  hydrocarbons  have  completely  separated  at  the  bottom  ; 
their  volume  is  read  off,  and  deducted  from  the  volume  of  the  crude 
phenol  employed. 

Having  found  this  method  to  be  untrustworthy,  the  author  en- 
deavoured to  work  out  a  volumetric  process  on  the  basis  of  the  well- 
known  reaction  of  phenol  with  bromine, — 

Cg  H5  0  H  +  3  Br,  =  Ce  Ho  Brs  0  H  +  3  H  Br. 

According  to  Landolt,  who  first  investigated  this  reaction,  so- 
lutions of  phenol  containing  but  1  part  in  43,700  parts  of  water  still 
produce  a  distinct  turbidity  on  the  addition  of  bromine  water.  As 
the  washing  and  drying  of  the  precipitated  tribromophenol  is  a 
tedious  operation,  the  reaction  does  not  aiford  a  handy  gravimetric 
method.  The  author  therefore  preferred  to  employ  an  excess  of 
weak  bromine  water,  and  to  determine  this  excess  volumetrically 
by  potassium  iodide,  and  standard  solution  of  sodium  hyposulphite. 
In  the  course  of  bis  experiments  he  found  that  nascent  bromine,  as 
liberated  from  a  mixture  of  potassium  bromide  and  bromate  by 
hydrochloric  acid,  is  preferable  to  bromine  water.  The  mixture  is 
produced  by  adding  bromine  in  moderate  excess  to  solution  of 
potassium  hydrate,  and  evaporating  to  dryness ;  the  residue  is  then 
dissolved  in  water,  and  the  available  bromine  determined  in  the 
solution  by  means  of  potassium  iodide,  hydrochloric  acid,  and 
sodium  hyposulphite. 

If  the  substance  under  examination  be  phenol  containing  water 
as  the  main  impurity,  it  may  be  dissolved  in  cold  water,  and  forth- 
with submitted  to  the  test.  But  if  the  amount  of  phenol  has  to  be 
determined  in  a  sample  of  coal-tar  creasote,  containing  many  hydro- 
carbons, agitation  with  warm  water  in  a  flask  is  required  to  insure  a 
complete  solution  of  the  carbolic  acid. 

The  results  obtained  by  the  author  are  very  satisfactory. 


122  YEAR-BOOK    OF    PHARMACY. 

Volumetric  Estimation  of  Magnesia  in  Potable  Waters.  L.  Leg- 
ler.  (Zi'if.filr  Anali/t.-Cheni.,  xv.,  425.)  The  method  recommended 
consists  mainly  in  the  precipitation  of  the  magnesium  as  hydrate 
by  a  known  quantity  of  sodium  or  potassium  hydrate,  and  the  titra- 
tion of  the  excess  of  caustic  alkali  by  standard  sulphuric  acid.  The 
reagents  required  are  a  solution  of  neutral  potassium  oxalate  (to 
precipitate  the  calcium),  decinormal  solutions  of  caustic  soda  and 
sulphui'ic  acid,  and  as  an  indicator  one  drop  of  rosolic  acid.  The 
modus  operandi  is  as  follows  : — 

The  expulsion  of  free  carbonic  acid,  and  the  complete  decom- 
position of  carbonates,  are  essential  points  in  this  process,  and  are 
best  accomplished  by  mixing  100  c.c.  of  the  water  with  decinormal 
sulphuric  acid  in  moderate  excess,  and  a  drop  of  the  indicator, 
allowing  the  mixtui'e  to  stand  for  some  time,  then  adding  a  slight 
excess  of  decinoi'mal  solution  of  sodium  hydrate,  boiling,  and 
making  careful  gradual  additions  of  standard  acid  to  the  boiling 
liquid,  until  it  becomes  permanently  colourless.  The  number  of  c.c. 
of  sulphuric  acid  used  are  calculated  for  carbonic  acid  or  lime. 
Boiling  the  water  "with  an  excess  of  acid  must  be  strictly  avoided. 

The  water  being  thus  freed  from  carbonates,  is  mixed  with  an 
excess  of  neutral  potassium  oxalate,  and  after  complete  precipitation 
of  the  lime,  it  is  boiled  with  a  known  volume  of  decinormal  NaH  0, 
to  effect  the  precipitation  of  the  magnesia,  and  then  made  up  to 
150  c.c.  by  the  addition  of  water.  After  filtering,  the  excess  of 
soda  is  estimated  in  100  c.c.  of  the  filtrate  by  adding  the  standard 
acid  in  the  same  manner  as  before. 

Magnesia  may  thus  be  estimated  in  waters  containing  only  two 
milligrams  of  Mg  0  per  litre,  besides  indefinite  quantities  of  lime 
and  alkalies. 

The  complete  removal  of  carbonates  is  necessary,  as  otherwise  the 
calcium  bicarbonate  contained  in  the  water  would  decompose  the 
potassium  oxalate,  forming  calcium  oxalate  and  potassium  bicarbo- 
nate, the  latter  of  which  would  require  an  increased  amount  of 
sulphuric  acid  for  neutralization,  and  thus  cause  a  serious  error  in 
the  analysis. 

Estimation  of  Tannin.  J.  Lowenthal.  (Zelt^chr.  filr  Analijt- 
Chem.,  xvi.,  33- i8.)  The  author  describes  the  results  of  his  experi- 
ments in  the  estimation  of  tannin,  and  considers  that  his  improve- 
ments give  determinations  satisfactory  for  technical,  if  not  for  strictly 
scientific,  purposes.  The  estimations  of  tannin  from  diff"crent  sources 
(e.g.,  sumach  and  nutgalls)  are  not  comparable,  but  only  those  from 
sumach  inter  se,  and  from  galls  inter  se. 


I 


PHARMACEUTICAL    CHEMISTRY.  123 

Hammer's  method  is  used,  the  extract  being  first  titrated  after 
adding  indigo  solution,  so  as  to  ascertain  its  potassium-permanganate 
value  ;  the  tannin  is  then  precipitated  from  another  portion  of  the 
extract,  and  the  permanganate-value  of  the  filtrate  ascertained  by 
the  difference  of  these  results. 

For  the  precipitation  of  the  tannin  a  solution  of  glue  in  water  is 
made  and  satnrated  with  common  salt;  it  contains  25  grams  of  glue 
to  the  litre.  After  thoroughly  mixing  this  with  the  tannin  extract, 
a  small  quantity  of  dilute  hydrochloric  or  sulphuric  acid  is  added  to 
assist  the  separation  of  the  tannin ;  a  vessel  with  narrow  opening 
should  not  be  used,  as  the  precipitate  coagulates  into  a  mass.  Of 
the  tannin-extract  to  be  titrated,  sufficient  is  taken  to  require  0'06 
to  0'08  grams  of  permanganate ;  10  gi-ams  of  sumach  are  extracted 
with  boiling  water,  and  after  cooling,  the  liquid  is  made  up  to  2 
litres.  To  100  c.c.  of  this  solution  100  c.c.  of  the  glue  solution  are 
added,  and  to  this  mixture  are  further  added  50  c.c.  of  water  con- 
taining 5  c.c.  of  H  CI  (1-12  sp.  gr.),  or  2  to  2-5  grams  of  Ho  S  0.^. 
The  sligbt  reducing  action  of  the  glue  solution  upon  the  perman- 
ganate may  be  safely  neglected ;  the  error  due  to  this  cause  is  less 
when  Hammei''s  powdered  skin  {hatdpidver^  is  employed.  This 
error  almost  vanishes  if  four-fifths  of  the  glue  solution  directed  to  be 
added  is  replaced  by  a  saturated  solution  of  common  salt.  The  pre- 
sence of  indigo  solution  is  necessary,  not  only  as  an  indicator,  but  it 
also  prevents  the  oxidising  action  of  the  permanganate  extending  to 
any  substances  in  the  extract  less  readily  oxidisable  than  the  indigo 
is  itself.  The  only  requisite  for  making  this  method  quite  accurate  is 
the  separation  of  pure  tannin  and  the  determination  of  its  permanga- 
nate-value ;  this  would  ensure  the  accurate  calculation  of  the  quan- 
tity of  tannin  from  the  difference  of  pei'manganate-values.  The 
sepai'ation  of  tannin  from  its  lead-compound  by  addition  of  insuffi- 
cient oxalic  acid  yielded  much  purer  tannin  than  the  separation  by 
sulphuretted  hydrogen. 

The  sample  in  which  tannin  is  to  be  estimated  is  never  dried  be- 
fore being  weighed,  as  it  is  sold  in  the  undried  state.  Oser's  re- 
commendation to  add  acid  during  the  titration  of  the  indigo  sokition 
has  been  accepted  by  the  author.  The  determination  of  glue  by 
precipitation  with  an  excess  of  tannin,  which  excess  is  afterwards 
titrated,  is  inexact.  Since  the  quantity  of  tannin  combining  with  a 
certain  quantity  of  glue  increases  with  the  quantity  of  tannin  pre- 
sent, the  author  intends  to  examine  the  effect  of  using  sodium-chloride 
solution  in  place  of  water.  Hydrochloric  acid  is  preferred  to  sul- 
phuric for  acidifying.     The  statements  of  Wagner  that  gall-tannin 


124  YEAR-BOOK    OF    PHARMACY. 

combined  with  glue  putrifies,  and  that  in  turkey-red  dye  works 
sumach  is  never  used  without  galls,  are  not  confirmed  by  the  au- 
thor's experience. 

Volumetric  Estimation  of  Alcohol.  T.  T.  Monell.  (Chem.  and 
Drugj.,  Dec,  1876,  from  Amer.  Chem.)  If  a  cobalt  salt  be  added  to 
an  alcoholic  solution  of  sulpho-cyanide  of  ammonium,  a  deep  blue 
coloration  is  produced,  which  suddenly  vanishes  on  dilution  with 
water,  and  reappears  on  further  addition  of  alcohol.  Given  the 
same  volume,  spirit  of  a  certain  percentage  always  gives  precisely 
the  same  intensity  of  colour  with  a  standard  blue  solution  in  which- 
ever order  alcohol  or  water  may  be  added.  It  is  possible  in  this 
way  to  determine  quickly,  by  a  volumetric  process,  even  so  little  as 
one-fourth  per  cent,  of  alcohol  in  a  mixture.  A  measured  quantity 
of  the  dark  blue  standard  fluid  is  placed  in  a  cylinder,  and  a  mix- 
ture to  be  tested  is  added  until  the  colour  is  reduced  to  that  of  a 
strip  of  pale  blue  glass  ;  the  volume  of  this  pale  coloured  fluid  will 
be  the  greater  as  the  mixture  is  richer  in  alcohol.  This  volume, 
once  determined,  will  always  remain  the  same,  and  the  percentage 
noted  on  the  cylinder  may  afterwards  be  read  off  without  further 
trouble.  The  standard  fluid  is  always  prepared  with  the  spirit  of 
the  same  strength,  and  compared  with  the  same  strip  of  blue  glass. 
The  nitrate  of  cobalt  is  the  salt  found  most  convenient  for  this  pur- 
pose. Coloured  brandy  may  be  tested  directly  ;  in  this  case  the  tint 
is  not  blue,  however,  but  green.  Two  cylinders  are  therefore  ne- 
cessary,— one  for  the  test,  and  one  to  give  the  desired  tint  in  conjunc- 
tion with  the  blue  glass.  The  cobalt  solution  may  be  either  neutral 
or  slightly  acid,  but  should  contain  as  little  water  as  possible. 

Cyclamin,  or  Arthanatin.  (Pharm.  Gentralhalle,  1877,  18.)  This 
glucoside  is  mentioned  by  Professor  de  Luca  as  a  substitute  for 
curare,  and  recommended  by  him  as  a  remedy  against  tetanus.  It 
is  contained  in  the  tubers  of  Cyclamen  EaropcBicm,  a  native  of  central 
and  south-eastern  Europe,  belonging  to  the  natui-al  order  Pnmu- 
lacece.  According  to  Saladin,  the  fresh  tubers  are  collected  in 
autumn,  crushed  into  a  pulp,  and  digested  with  a  small  quantity  of 
water.  The  solution  is  evaporated  at  a  temperature  not  exceeding 
60°  C.  to  the  consistence  of  a  syrup,  the  residue  exhausted  with 
absolute  alcohol,  the  alcoholic  solution  decolorized  with  animal 
charcoal,  and  allowed  to  evaporate  spontaneously  in  a  warm  place. 

Cyclamin  thus  prepared  forms  white  odourless  crystals  having  a 
very  acrid  taste.  It  is  readily  soluble  in  water  and  alcohol,  but  in- 
soluble in  ether,  chloroform,  and  carbon  bisulphide.  The  aqueous 
solution,  according  to  De  Luca,  froths  like  a  solution  of  soap ;  and 


PHAEMACEUTICAL   CHEMISTRY.  125 

when  heated  to  60°-70°  C,  it  separates  the  cyclamin  in  a  coagulated 
form.  With  concentrated  sulphuric  acid  it  forms  a  yellow  solution, 
passing  gradually  to  violet.  When  boiled  with  dilute  mineral  acids 
it  is  split  up  into  glucose  and  a  resinoid  substance  called  cyclamiretin, 
which  is  insoluble  in  water  and  in  ether,  but  soluble  in  alcohol.  The 
same  decomposition  is  effected  by  emulsin  at  30°-35°  C. 

The  formula  of  cyclamin  was  ascertained  to  be  Coo  -^"vt  Oio- 

According  to  Pelikan,  who  administered  this  substance  to  frogs, 
both  internally  and  by  subcutaneous  injections,  it  belongs  to  the 
irritant  poisons.  Schroff  observed  that  the  toxic  symptoms  follow- 
ing the  internal  administration  of  0'2  gram  passed  off  in  the  course 
of  an  hour. 

The  Detection  of  Bile  in  Urine.  0.  Kosenbach.  (Med.  Central- 
hiatt.}  Urine  containing  bile,  when  passed  through  white  filtering 
paper,  imparts  a  yellow  or  brown  colour  to  the  paper.  On  allowing 
one  drop  of  strong  nitric  acid  to  run  down  the  side  of  the  moist 
filter,  it  leaves  a  yellow  streak,  soon  changing  to  orange,  with  a 
violet  border,  on  the  outside  of  which  blue  and  emerald  green  zones 
may  be  observed  :  these  colours  remain  visible  for  some  time.  Dark 
coloured  urine,  owing  its  tint  to  substances  other  than  bile,  do  not 
produce  this  play  of  colours. 

The  Detection  of  Sulphur  in  Organic  Compounds.  H.  Vohl. 
(Bar.  der  deutsch.  Chem.-Ges.,  ix.,  875.)  The  tests  generally  ap- 
plied for  the  detection  of  sulphur  in  organic  substances  afford  no 
means  of  distinguishing  between  sulphur,  as  such,  and  its  oxygen 
compounds.  The  author's  process  is  not  open  to  the  same  objection, 
as  it  is  based  upon  a  reaction  which  is  not  shared  by  these  oxygen 
compounds. 

The  test  solution  is  prepared  by  introducing  freshly  prepared  cal- 
cium hydrate,  in  small  quantities  at  a  time,  into  a  flask  containino- 
a  mixture  of  two  volumes  of  pure  glycerin  and  one  volume  of  dis- 
tilled water,  until  a  saturated  solution  is  obtained ;  then  adding 
hydrate  of  lead,  or  finely  powdered  letharge,  in  excess ;  boiling  the 
mixture  for  a  few  minutes,  allowing  it  to  settle  in  the  closed  flask, 
and  decanting  the  clear  liquid  from  the  sediment. 

Organic  substances  containing  sulphur,  such  as  hairs,  feathers, 
nails,  horn,  albumen,  blood-serum,  etc.,  when  heated  with  this  solu- 
tion, are  blackened,  owing  to  the  formation  of  sulphide  of  lead. 
Volatile  compounds  require  to  be  heated  with  the  reagent  in  a 
sealed  tube  to  10o°-110°  C.  for  several  hours. 

The  test  is  a  very  delicate  one,  as  may  be  seen  from  the  fact  that 
■wheat  bread,  when  boiled  with  the  reagent,  assumes  a  yellow  and 


126  YEAR-BOOK    OP    PHARMACY. 

afterwards  a  grey  colour,  the  reaction  being  due  in  this  case  to  the 
trace  of  sulphur  contained  in  the  gluten  of  the  wheat.  Blood  stains 
on  linen,  and  also  the  stains  of  seminal  fluid,  are  blackened  on  being 
moistened  with  the  reagent  and  heated  to  100°  C. 

Solutions  of  hydrate  of  lead  in  caustic  potash  or  soda  will,  of 
course,  produce  the  same  effect ;  but  they  are  not  so  well  suited  for 
this  test,  on  account  of  the  yellow  or  brown  coloration  which  the 
caustic  alkalies  impart  to  many  organic  substances. 

Impurities  in  Wood  Charcoal.  M.  Jaillard,  (Joum.  de  Pharm. 
et  de  Chim.,  xxv.,  121.)  Vegetable  charcoal  frequently  contains 
organic  impurities  which  have  escaped  destruction  during  its  pre- 
paration. The  commonest  of  these  is  acetate  of  potash,  of  which 
the  author  has  found  some  samples  to  contain  as  much  as  0*3  per 
cent.  Such  a  charcoal  requires  to  be  heated  to  redness  in  a  closed 
vessel  to  free  it  from  its  organic  constituents. 

Preparation  of  Pure  Potassium  Cyanide.  E.  Erlenmeyer. 
(Zeitschr.  des  oesterr.  Apoth.  Ver.,  1877,  -iO,  from  Ber.  der  deutsch. 
Chem.-Ges.)  The  process  of  fusing  a  mixture  of  ferrocyanide  and  car- 
bonate of  potassium  yields  a  preparation  containing  a  considerable 
amount  of  cjanate,  which  is  difficult  to  remove.  By  using  metallic 
potassium  in  place  of  the  carbonate,  the  formation  of  cyanate  is 
completely  prevented,  and  a  pure  cyanide  obtained.  As  cyanide  of 
sodium,  or  a  mixture  of  cyanide  of  potassium  and  sodium,  will  serve 
for  most  of  the  purposes  for  which  the  potassium  salt  is  generally 
employed,  the  author  suggests  the  use  of  metallic  sodium  (as  being 
much  cheaper  than  potassium)  for  the  preparation  of  a  pure  alkaline 
cyanide.  The  composition  of  the  product  thus  obtained  would  be 
represented  by  the  formula  2  K  Cy  +  Na  Cy. 

The  Determination  of  Soda  in  Pearl  Ash  by  Indirect  Analysis. 
G.  C.  Wittstein.  (Zeitschr.  des  oesterr.  Apoth.  Ver.,  1877,  207.) 
In  estimating  the  potassium  and  sodium  in  a  mixture  of  their  car- 
bonates by  the  so-called  indirect  method,  it  was  hitherto  the  rule 
first  to  convert  these  carbonates  into  chlorides  or  sulphates.  This 
the  author  shows  to  be  unnecessary,  as  the  relative  proportions  of 
the  two  carbonates  may  be  equally  well  calculated  from  the  quantity 
of  carbonic  acid  which  the  mixture  is  found  to  contain.  If  the 
carbonic  acid  (C  0.,)  amounts  to  more  than  31'80  per  cent.,  or  to 
less  than  41'47  per  cent.,  the  alkaline  carbonate  under  examination 
can  neither  be  pure  potassium  carbonate,  nor  pure  sodium  carbonate, 
but  must  be  a  mixture  of  the  two,  the  composition  of  which  can  be 
ascertained  by  the  following  calculation  : — 

To  find  the  per  centage  of  potash  (K,  0),  multiply  the  weight  of 


PHARMACEUTICAL   CHEMISTRY.  12  7 

the  two  bases  (the  total  weight  of  the  carbonates  minus  that  of 
C  Oj)  by  1-708763,  deduct  the  product  from  the  weight  of  the 
carbonates,  and  divide  the  rest  by  -  0  2426G3. 

To  find  the  percentage  of  soda  (Na^  0),  multiply  the  weight  of 
the  bases  by  1 -466100,  deduct  from  the  product  the  weight  of  the 
carbonates,  and  divide  the  rest  by-0'242663. 

Eeactions  of  Trimethylamine  with  Solutions  of  Metallic  Salts. 
C.  Vincent.  (Bull,  de  la  Soc.  Chim.  tie  Paris,  1877,  194.)  The 
addition  of  an  aqueous  solution  of  trimethylamine  to  metallic  solu- 
tions produces  the  following  reactions  : — 

Magnesium  Salts. — With  neutral  solutions  of  magnesium  salts  the 
reagent  produces  a  white  permanent  precipitate ;  no  precipitation 
occurs  with  acid  solutions,  but  on  the  subsequent  addition  of  sodium 
phosphate,  a  white  amorphous  precipitate  is  formed,  which  gradually 
becomes  crystalline. 

Berylliiim  Salts. — White  permanent  precipitate. 

Aluminiiom  Salts. — Gelatinous  precipitate,  soluble  in  an  excess  of 
the  reagent. 

Zirconium  Salts. — White  permanent  precipitate. 

Cerious  Salts. — White  permanent  precipitate. 

Ceric  Salts. — Reddish  white  permanent  precipitate. 

Ferrous  Salts. — Dirty  white  permanent  precipitate. 

Ferric  Salts. — Brown  permanent  precipitate. 

Chromiuvi  Salts. — With  green  solutions,  a  grey  permanent  pre- 
cipitate ;  with  violet  solutions,  a  bluish  green  one. 

Manganous  Salts. — White  precipitate,  turning  brown  on  exposure 
to  the  air.     The  precipitation  occurs  also  with  acid  solutions. 

Cobalt  Salts. — Bluish  grey  permanent  precipitate. 

JVickel  Salts. — Pale  green  permanent  precipitate. 

Uranium  Salts. — Yellow  permanent  precipitate. 

Zinc  Salts. — White  permanent  precipitate. 

Stannous  Salts. — White  permanent  precipitate. 

Stannic  Salts. — White  permanent  precipitate,  soluble  in  an  excess 
of  the  reagent. 

Bismuth  Salts. — White  permanent  precipitate. 

Lead  Salts. — With  lead  nitrate  a  white  precipitate,  soluble  in  an 
excess  of  the  reagent.     With  lead  acetate,  no  precipitate. 

Cupric  Salts. — Greenish  blue  permanent  precipitate. 

Mercurous  Salts. — Black  permanent  precipitate. 

2Lercuric  Salts. — Yellow  permanent  precipitate ;  with  mercuric 
chloride  the  reaction  is  the  same  as  with  other  mercuric  salts. 

Silver  Salts. — Dark  grey  precipitate,  soluble  in  a  large  excess  of 


128  YEAR-BOOK    OF    PHARMACY. 

the  precipitant.    Silver  chloride  is  completely  insoluble  in  trimethyl- 
amine. 

Palladium  Salts. — Brown  precipitate,  soluble  in  an  excess  of  the 
reagent. 

Gold  Salts. — Pale  yellow  precipitate,  also  soluble  in  an  excess. 

Flatinum  Salts. — Yellow  precipitate,  soluble  in  hot  water,  and 
crystallizing  from  the  solution  on  cooling. 

The  Detection  of  Nitrates  in  Potable  Waters.  A.  Vogel. 
(Neues  Repertor.fiir  Phann.,  xxiv.,  G66.)  The  author  employs  leaf 
gold  for  the  detection  of  nitrates  in  potable  water.  20  c.c.  of  the 
water  to  be  tested  are  evaporated  in  a  porcelain  dish,  with  gold  leaf 
and  a  few  c.c.  of  pure  hydrochloric  acid.  If  nitrates  are  present, 
some  of  the  gold  will  be  dissolved,  and  may  be  detected  in  the  solu- 
tion by  stannous  chloride ;  or  if  the  quantity  of  nitrates  is  not  too 
small,  by  the  yellow  colour  of  the  solution.  The  advantage  of  this 
method  consists  in  the  non-employment  of  sulphuric  acid,  the  im- 
purities of  which  (nitric  acid,  and  oxides  of  nitrogen)  are  a  veiy 
common  source  of  error  in  testing  for  traces  of  nitrates. 

Preparation  of  Pure  Hydriodic  Acid.  H.  Kolbe.  {Jour n.  f. 'pr aid. 
Chem.,  XV.,  1"2.)  One  part  of  ordinary  phosphorus  is  gradually 
added  to  ten  parts  of  iodine  in  a  retort  filled  with  carbonic  acid  gas ; 
the  resulting  liquid  is  heated  for  a  short  time,  then  allowed  to  cool, 
mixed  with  four  parts  of  water  and  distilled.  The  acid  thus  obtained 
is  colourless  and  free  from  uncombined  iodine.  The  application  of 
larger  proportions  of  iodine  and  water,  as  recommended  in  "  Gmelin's 
Handbuch,"  and  other  works,  results  in  the  production  of  a  much 
weaker  acid,  which  moreover  always  contains  free  iodine. 

Volumetric  Determination  of  Carbonic  Acid.  G.  W.  Wigner. 
{Analyst,!.,  158;  Journ.  Chem.  Soc,  1S77,  218.)  Most  laboratories 
are  now  furnished  with  the  McLeod  appai'atus,  or  some  similar 
efficient  apparatus,  far  measuring  the  volume  of  gases  under  known 
conditions  of  temperature  and  pressure.  The  author  has  therefore 
devised  a  simple  apparatus  for  the  decomposition  of  carbonates,  and 
the  measuring  of  the  gas  evolved.  A  test-tube  of  about  7  inches 
by  1  inch  is  taken  and  provided  with  a  good  india-rubber  stopper 
bored  with  two  holes.  Through  one  of  these  holes  a  tubulated, 
thistle-headed  funnel  of  small  size,  furnished  with  a  stop-cock,  is 
passed,  and  through  the  other  a  bent  piece  of  small-bore  glass-tubing, 
also  provided  with  a  stop-cock.  This  bent  tube  is  coupled  to  the 
McLeod  or  other  gas-measurment  apparatus  by  a  short  length  (6 
inches)  of  very  stout,  small-bore  india-rubber  tube  (y'g  inch  is  large 
enough  for  the  bore  of  this).     In  the  bowl  of  the  thistle-funnel  a 


PHARMACEUTICAL   CHEMISTRY.  129 

glass  marble  is  put,  and  in  the  interior  of  the   test-tube  a  smaller 
test-tube  of  about  2  in.  x  -|  in.,  containing  the  sample  to  be  analysed. 
The  process  is  as  follows : — The  tubes  of  the  McLeod  apparatus  are 
filled  with  mercury  and  the  stop-cocks  closed.     The  sample  (say  25 
grams  of  carbonate  of  lead)    is   weighed  and   transferred   to    the 
smaller  tube,  and  about  half  an  ounce  of  distilled  water  is  poured 
into  the  large  test-tube.     The  small  tube  is  then  carefully  dropped 
in,  taking  care  that  its  mouth  is   above  the  level  of  the   water  in 
the  large  tube ;  the  stopper  into  which  the  funnel  and  bent  tube 
have  been  inserted  is  then  carefully  put  in  place,  and  the  whole 
held  in  a  slightly  oblique  position  in  a  retort-stand  clamp,  on  the 
ordinary  rising  table  of  the  McLeod  apparatus.     The  india-rubber 
tube  is  then  coupled  up  to  the  facets  of  the  measuring-tube  of  the 
McLeod   apparatus.     The   stop-cock   on    the   bent   tube  is    closed, 
after  having  opened  it  and  the  cock  on  the  funnel-tube  in  order 
to    liberate  any  excess    of  air  in  the   india-rubber   tube,    and   the 
mercury  in  the  measuring-tube  is  allowed  to  fall,  so  as  to  produce 
a   vacuum.     The  stop- cock    on   the   funnel    remains  open,  and  to 
the  bottom  of  the  test-tube  a  lamp  is  applied  until  the  water  boils 
briskly,  when  distilled  water  is  poured  into   the  funnel  and  kept 
from  running  into  the  test-tube  by  the  pressure  of  steam  ;  the  boil- 
ing is  continued  until  the  steam  escaping  through  the  funnel  and 
under  the  glass  marble  all  condenses,  showing  that  the  tube  is  filled 
with  pure  steam.     The  lamp  is  now  withdrawn  and  the  stop-cock 
instantly  closed.     Meanwhile  a  portion  of  dilute  nitric  acid  has  been 
boiled  on  another  burner,  and  is  poured  into  the  funnel.     The  stop- 
cocks  on  the  bent  tube  and  on  the  measuring-tube  are  opened,  and 
then  the  stop-cock  on  the  funnel-tube  is  cautiously  opened.     The 
hot  acid  of  course  runs  in,  and  the  only  precaution  necessary  is  to 
avoid  liberating  the  gas  too  quickly.     When  the  test-tube  is  about 
two-thirds  full,  and  all  effervescence  has  ceased,  the  solution  in  the 
tube   is  again  boiled,  and  then,  still  maintaining  a  partial  vacuum 
by  means  of  the  mercury,  the  tube  is  filled  completely  through  the 
funnel-tube  with  boiling  distilled  water,  until  every  bubble  of  air  is 
driven  into  the  measuring-tube  of  the  McLeod  apparatus.    The  stop- 
cock on  the  bent  tube  is  then  shut,  and  the  mercury  in  the  pressure- 
tube  and  the  measuring-tube  brought  to  the  same  level.  This  brings 
the  internal  pressure  of  the  air  on  the  short  india-rubber  connecting 
tube  to  the  atmospheric  pressure,  and  as  its  volume  does  not  exceed 
1   c.c.   the  correction  for  its  temperature  may  be  safely  omitted. 
The  gas  is  then  measured  in  the  ordinary   way,  and  its  volume 
calculated  to  weight  and  percentage. 

K 


130  TEAE-BOOK    OF    PHARMACY. 

It  is  easy  to  make  four  determinations  of  carbonic  acid  per  hour 
by  this  apjiaratus,  and  the  accuracy  of  the  results  is  very  great. 

Determination  of  Morphine  in  Opium.  E.  F.  Teschemacher. 
{Chem.  News,  xxxv.,  47;  Journ.  Ghent.  Soc,  1877,  231.)  In  employ- 
ing the  following  method,  the  use  of  alcohol  to  extract  the  morphine 
is  avoided,  and  mecouic  acid  is  separated  at  an  early  stage,  which 
prevents  the  formation  of  a  basic  meconate  on  precipitation  of  the 
morphine.  Two  special  reagents  are  required  for  this  process  :  the 
one  prepared  by  mixing  1  part  of  solution  of  ammonia,  sp.  gr.  0880, 
with  20  parts  of  methylated  alcohol  and  digesting  in  this  mixture  a 
large  excess  of  morphine,  this  when  filtered  is  termed  "  morplnated 
spirit;"  the  other,  '■'' morphiated  loater,"  is  water  saturated  with 
excess  of  morphine,  and  contains  004  per  cent,  of  this  alkaloid. 

1000  grains  of  opium  are  macerated  for  twelve  to  twenty  hours 
in  about  4000  grains  of  cold  distilled  water,  together  with  300 
grains  of  lead  acetate,  stirring  the  mixture  from  time  to  time.  This 
separates  the  meconic  acid  as  lead  meconate,  whilst  the  morphine  is 
dissolved  in  the  acetic  set  free. 

After  this  maceration  the  opium  may  be  readily  ground  in  a  mortar 
to  a  paste,  and  so  much  more  cold  distilled  water  added  (rinsing  the 
pestle  and  mortar  with  successive  portions  of  it)  as  to  fill  with  the 
mixture  a  measure  =  20,250  grains  of  distilled  water :  experience 
has  shown  that  the  space  occupied  by  the  insoluble  matters  measures 
from  200  to  300  grains,  so  that  the  limit  of  possible  error,  by  aver- 
aging and  allowing  250  grains  for  the  insoluble  portion,  amounts  to 
0  05  per  cent,  in  opium  containing  10  per  cent,  of  morphine.  The 
mixture  is  to  be  filtered  and  15,000  measured  grains  (  =  750  grains 
of  opium)  of  the  clear  solution  are  to  be  evaporated  to  an  extract  on 
a  water  bath,  and  this  residue  to  be  drenched  with  3O90  grains  of 
boiling  alcohol  or  methylated  spirit,  and  the  whole  digested,  with 
frequent  stirring,  for  about  ten  minutes.  This  separates  the  gum, 
etc.,  of  the  opium,  which  is  insoluble  in  alcohol,  and  so  far  frees  the 
solution  of  morphine  from  impurity.  At  this  stage  of  the  process  it 
is  well  to  get  rid  of  the  excess  of  lead-salts,  and  for  this  end  sul- 
phuric acid  is  preferable  to  sulphuretted  hydrogen.  So  much  diluted 
sulphuric  acid  as  may  be  equal  to  30  grains  of  oil  of  vitriol  will 
almost  always  be  sufficient  for  this  purpo.se,  any  excess  of  acid  being 
converted  into  sulphate  of  ammonia  by  the  subsequent  addition  of  so 
much  solution  of  ammonia  as  shall  be  equivalent  to  the  30  grains  of 
oil  of  vitriol,  thus  forming  a  salt  but  slightly  soluble  in  the  alcoholic 
solution.  This  mixture  may  now  be  transferred  to  a  beaker  and 
allowed  to  settle  for  twelve  hours,  after  which  it  is  to  be  filtered,  and 


PHAEMACaUTICAL    CHEMISTRY.  131 

the  filter  and  insoluble  residue  thorouglily  washed  with  alcohol  or 
methylated  spirit.  This  alcoholic  filtrate  is  then  distilled,  or  eva- 
porated on  a  water  bath,  to  about  1000  grains  ;  and  mixed,  while 
still  hot,  with  400  grains  of  solution  of  ammonia,  sp.  gr.  0'880,  stir- 
ring rapidly  and  continuously  for  at  least  twenty  minutes,  whilst 
the  beaker  or  evaporating  dish  should  be  cooled  as  rapidly  as  pos- 
sible, by  immersion  in  an  external  vessel  filled  with  cold  water.  The 
rapid  and  continuous  stirring  is  most  important,  as  the  precipitation 
of  the  whole  of  the  morphine  in  fine  powder  is  thereby  effected, 
instead  of  the  granular  or  mammillated  condition  so  frequently  met 
with,  and  it  thus  permits  of  the  easy  and  thorough  separation  of  all 
the  narcotine  which  may  be  mixed  with  the  morphine.  When  the 
cooling  of  the  mixture  and  precipitation  of  the  morphine  is  thus 
attained,  transfer  it  quickly  and  completely  to  a  filter  of  sufficient 
capacity  to  hold  the  whole,  and  when  the  liquid  portion  has  passed 
through,  wash  the  remainder  of  the  precipitated  morphine  adhering 
to  the  dish  or  beaker  on  to  the  filter,  using  for  this  purpose  the 
morphiated  spirit  already  described,  and  continuing  the  washing  of 
the  precipitate  until  it  is  completely  fi^ed  from  the  mother-liquor. 
To  do  this  efiPectually  requires  some  little  care  :  thus  the  morphine 
on  the  filter  must  be  kept  in  a  spongy  condition  and  never  allowed 
to  cohere,  which  is  easily  effected  by  pouring  the  morphiated  spirit 
round  the  edges  of  the  filter  so  as  not  to  disturb  the  precipitate, 
which  must  not  be  permitted  to  drain  or  solidify  until  this  washing 
is  completed. 

The  precipitate  is  now  to  be  washed  from  off"  the  filter-paper  with 
the  morphiated  water  previously  described,  and  digested  therein  for 
a  few  minutes,  which  removes  some  more  colouring  matter  together 
with  any  salts  soluble  in  water  but  insoluble  in  alcohol,  which  may 
have  adhered  to  the  precipitated  morphia;  then  once  more  collect 
the  precipitate  on  a  filter,  washing  it  with  morphiated  spirit,  after 
this  once  with  ether,  and  finally  thrice  or  more  with  benzin ;  this 
completely  frees  it  from  narcotine,  which  is  very  soluble  in  benzin, 
morphine  on  the  contrary  being  insoluble  in  this  liquid.  It  now 
remains  to  drain  and  dry  at  a  low  temperature,  say  100°  F.,  the 
resulting  pure  and  white  morphine,  the  weight  of  which  will  indi- 
cate the  amount  of  this  alkaloid  present  in  750  grains  of  the  opium 
under  examination. 

Extraction  of  Caflfeine  from  Guarana.  Dr.  F.  V.  Greene.  (Amer. 
Journ.  Phann.,  1877,  338.)  In  determining  the  percentage  of  caf- 
feine in  guarana  by  Stenhouse's  process  (see  Pharm.  Journ.,  1st  series, 
xvi.,  212),  the  author  experienced   some  diflBcalty  in  separating  the 


132  YEAR-BOOK    OF    PHARMACY. 

solution  from  the  portion  insoluble  in  boiling  water,  and  found  the 
washing  of  the  mass  precipitated  by  lead  acetate  a  very  tedious 
operation.  He  therefore  attempted  the  separation  of  the  alkaloid  by 
means  of  litharge,  which  substance  has  been  recommended  by  Prof. 
E.  S.  "Wayne  for  the  extraction  of  caffeine  from  coffee  and  tea.  The 
results  proved  that  in  the  case  of  guarana,  too,  this  process  affords 
a  ready  means  for  the  isolation  and  estimation  of  the  alkaloid. 

The  details  of  the  method  are  as  follows  : — The  powdered  guarana 
is  intimately  mixed  with  three  times  its  weight  of  finely  divided 
litharge,  and  the  mixture  boiled  in  distilled  water,  the  ebullition 
being  continued  until,  on  allowing  the  temperature  to  fall  below 
the  boiliug  point,  the  insoluble  portion  is  found  to  subside  rapidly, 
leaving  the  supernatant  liquid  clear,  bright,  and  without  colour. 
The  quantity  of  distilled  water  required  will  be  found  to  be  about  a 
pint  for  every  fifteen  grams  of  the  guarana  used  in  the  experiment, 
and,  as  the  boiling  has  to  be  continued  for  several  hours  before  the 
desired  and  all  essential  separation  mentioned  above  takes  place, 
water  must  be  added  from  time  to  time  to  supply  the  place  of  that 
lost  by  evaporation.  When  cool,  the  clear  liquid  is  decanted  upon 
a  filter,  and  when  it  has  passed  through,  which  it  will  be  found  to 
do  with  fiicility,  the  precipitate  is  to  be  transferred  to  the  filter  and 
washed  with  boiling  water,  the  washing  to  be  continued  as  long  as 
yellowish  precipitates  are  produced  with  either  phosphomolybdic 
acid  solution,  auric,  or  platinic  chloride.  A  stream  of  sulphuretted 
hydrogen  gas  is  now  passed  through  the  filtrate  to  remove  the  small 
quantity  of  lead  that  has  been  dissolved  and  the  sulphide  thus 
formed  separated  by  filtration.  The  solution  is  evaporated  on  a 
water  bath  to  expel  the  excess  of  sulphuretted  hydrogen,  filtered  to 
remove  a  trace  of  sulphur,  finally  evaporated  to  the  crystallizing 
point,  and  the  caffeine,  which  crystallizes  out  on  cooling,  removed 
from  the  mother  liquor  and  pressed  between  folds  of  bibulous  paper. 
After  being  thus  treated,  the  crystals  will  be  found  to  be  perfectly 
white.  On  diluting  the  mother  liquor  with  distilled  water,  filtering 
and  evaporating,  a  second  crop  of  crystals  are  obtained,  which  ai"e 
also  perfectly  white,  after  being  pressed  as  above.  The  crystals  are 
now  dissolved  in  boiling  diluted  alcohol,  filtered,  and  the  solution 
set  aside  to  crystallize  by  spontaneous  evaporation.  The  resulting 
crystals  of  caffeine  are  perfectly  pure  and  colourless. 

In  order  to  test  the  accuracy  of  the  process,  fourteen  grams  of 
guarana  in  an  impalpable  powder  were  treated  with  the  utmost  care, 
as  above  described.  The  extracted  caffeine,  after  drying  at  100°  F. 
until  the  weight  became  constant,  was  found  to  weigh  •707  grams, 


PHARMACEUTICAL   CHEMISTRY.  133 

5"0j  per  cent.,  a  remarkably  close  approximation  to  the  results  of 
Stenhouse,  who  from  25  grams  of  guarana,  obtained  1"2G0  grams  of 
caffeine  =  504  per  cent.,  and  from  14  grams  5*1  per  cent.  Average 
=  5-07. 

As  this  method  of  extracting  caffeine  is  entirely  devoid  of  all 
complicated  steps,  and  requires  but  a  short  space  of  time  for  its 
completion,  it  may  be  used  advantageously  in  estimating  the  per- 
centage of  caffeine  in  the  fluid  extract  of  guarana,  -which  is  now 
frequently  prescribed. 

Rapid  Preparation  of  Caffeine.  0.  Caillol  and  P.  Cazeneuve. 
(Bull.  Soc.  Chim.,  1877,  199.)  Caffeine  is  generally  prepared  from 
tea,  as  it  is  contained  therein  in  larger  quantities  than  in  coffee. 
According  to  the  usual  method,  the  tea  is  exhausted  with  water,  the 
infusion  precipitated  by  lead  acetate,  the  filtrate  freed  from  lead  by 
sulphuretted  hydrogen,  and  evaporated ;  the  crystals  thus  obtained 
are  purified  by  decolorization  with  animal  charcoal  and  recrystal- 
lization. 

The  authors  have  attained  a  better  result  by  the  following  more 
rapid  process  : — Black  tea  is  thoroughly  softened  with  four  times  its 
weight  of  hot  water  ;  a  quantity  of  calcium  hydrate  equal  to  that  of 
the  tea  used  is  then  added,  and  the  whole  evaporated  on  a  water 
bath  to  perfect  dryness.  The  dry  residue  is  exhausted  with  chloro- 
form in  a  displacement  apparatus,  and  the  chloroform  recovered 
from  the  percolate  by  distillation.  The  residue  left  in  the  retort  is 
a  mixture  of  caffeine  and  a  resinous  substance  containing  chloro- 
phyll. On  treating  it  with  hot  water,  filtering,  and  evaporating  the 
filtrate  on  a  water  bath,  the  caffeine  is  obtained  in  perfectly  white 
silky  crystals. 

Improvements  in  the  Manufacture  of  Sodium  Carbonate.  Dr.  H. 
Hager.  (Pharm.  Centralhalle,  1877,  42.)  The  prepai'ation  of 
carbonate  of  soda  by  the  so-called  ammonia  process,  though  com- 
paratively new,  is  already  undergoing  important  modifications. 
Hitherto  the  main  step  in  the  process  was  the  formation  of  sodium 
bicarbonate  (see  Year-Booh  of  Pharmacy,  1874).  The  latest  modi- 
fication is  based  upon  the  comparative  insolubility  of  the  monohy- 
drated  sodium  carbonate,  Nao  C  O3.  Hj  0,  in  a  concentrated  solution  of 
common  salt.  The  ordinary  carbonate,  usually  containing  10  molecules 
of  water  of  crystallization,  when  recrystallized  at  35°  C.  contains 
but  seven  molecules,  and  when  crystallized  at  60°-70°  C.  it  contains 
but  one  molecule  of  water.  The  action  of  the  ammonium  carbonate 
upon  the  sodium  chloride  is  explained  by  the  following  equation  •'  — 
2  Na  CI  +  (N  HJ2  C  O3  -  Nao  C  O3  +  2  N  H^  CI. 


134  TEAR-BOOK   OF    PHARMACY. 

Dialysed  Iron.  A.  and  H.  C.  Blare.  (Amer.  Journ.  PJiarm., 
1877,  oiO.)  This  prepai-ation  has  attracted  the  attention  of  many 
members  of  the  medical  and  pharmaceutical  professions  for  some 
time  past,  and  the  experience  resulting  from  its  use  is  so  satisfactory 
that  it  promises  to  become  one  of  the  most  valued  therapeutic  agent.s 
in  a  large  class  of  diseases  where  the  ordinary  iron  preparations  are 
objectionable.  The  writers  obtained  the  following  formula  from  a 
prominent  French  chemist  who  has  been  extensively  engaged  in  the 
manufacture  of  this  remedy  : — 

Take  10  parts  liq.  ferri  per.  chlor.  (B.  P.),  precipitate  by  aqua 
ammonisB,  and  wash  the  precipitate  thoroughly.  Mix  this  with  12 
parts  of  liq.  ferri  per.  chlor.  (B.P.),  and  place  in  a  dialyser.  The 
dialyser  is  placed  in  a  suitable  vessel  with  distilled  water,  the  water 
under  it  renewed  every  24  hours.  The  opei*ation  is  continued  until 
the  dialysate  ceases  to  contain  chlorine,  at  which  time  the  pre- 
paration is  found  to  be  neutral.  It  usually  takes  from  12  to  15 
days  to  complete  the  process. 

The  resulting  preparation  is,  or  should  be,  of  a  deep  dark  red 
colour,  and  contains  about  5  per  cent,  of  the  oxide  of  iron.  As  to 
the  chemical  condition  of  the  iron  in  solution,  M.  Bravais,  of  Paris 
(who  claims  to  produce  the  only  genuine),  says,  "  It  consists  of 
liquid  peroxide  of  iron,  i.e.,  iron  merely  united  with  oxygen  and 
water  to  the  exclusion  of  all  acids ; "  but  it  is,  no  doubt,  in  fact  a 
neutral  solution  of  an  oxychloride  of  iron  in  a  concentrated  form, 
and  the  theory  of  its  production  is  nothing  new,  and  is  very  simple. 
The  oxychloride  (which  is  the  substance  retained  in  solution  in  the 
dialyser)  is  a  colloidal  substance.  The  chloride  (which  is  the  princi- 
pal substance  rejected,  or  washed  out  as  it  were)  is  a  crystalloidal 
substance.  These  two  substances — crystalloid  and  colloid — are 
separated  by  dialysis,  the  former  from  the  latter  by  diffusion  through 
a  septum,  such  as  parchment  paper. 

Other  formulae  more  recently  have  been  suggested,  differing 
somewhat  from  the  above,  and  it  has  been  the  subject  of  no  little 
discussion  abroad  as  to  the  particular  merits  of  the  one  or  the  other 
of  these.  By  some  it  has  been  suggested  to  pursue  the  following 
formula  : — Take  a  given  quantity  of  liq.  ferri  perchlor.  (B.  P.),  and 
precipitate  by  ammonia;  wash  well  the  precipitate,  and  mix  with 
sufficient  quantity  of  the  same  preparation  of  liq.  ferri  perchlor.  to 
saturation,  and  dialyse.  It  is  remarkable  how  large  a  proportion  of 
this  freshly  precipitated  sesquioxide  of  iron  will  be  taken  up  or 
dissolved.  For  example,  the  precipitate  obtained  from  one  pint  of 
our  officinal  liquor  ferri  chlor.,  representing  3  ounces  and  G  drams 


PHARMACEUTICAL   CHEMISTRY.  135 

of  dry  oxide,  is  entirely  taken  up  by  about  5  fluid  ouncef?  of  the 
same  liquor.  In  the  magma  this  precipitate  seems  a  very  great 
quantity,  so  bulky  is  it ;  and,  as  stated  before,  it  is  quite  surprising 
to  see  it  disappear  into  solution  under  the  influence  of  so  small  a 
quantity  of  the  liquor. 

By  following  the  above  method  the  process  is  shortened  consider- 
ably. It  became  thoroughly  dialysed  in  one  week,  while  the  other 
takes  about  twice  that  time. 

Still  another  method  has  been  suggested,  namely,  to  take  a  given 
quantity  of  the  liquor  ferri  chlor.,  and  add  aqua  ammonite  almost 
enough  to  produce  the  precipitate  of  the  sesquioxide.  When  the 
precipitating  point  is  reached  the  whole  solution  is  placed  in  the 
dialyser.  The  chloride  of  ammonium  is  thus  extracted  from  the 
solution,  and  the  peroxide  of  iron,  or  oxychloride,  retained. 

If  either  of  these  processes  is  pursued  carefully,  the  same  result 
will  be  obtained.  If  the  solution,  after  completion  of  the  operation, 
should  contain  more  than  5  per  cent,  of  iron,  it  may  be  diluted  with 
distilled  water  till  it  reaches  that  point.  There  are  some  dialysed 
irons  in  the  market  containing  no  more  than  from  3|  to  4  per 
cent.  When  the  preparation  has  become  thoroughly  dialysed,  it 
is  tasteless  and  neutral ;  the  operation  should  then  be  discontinued, 
as  by  further  dialysis  the  liquid  is  converted  into  a  gelatinous 
condition. 

The  above  formula  furnishes  an  article  precisely  similar  to  the 
original  Bravais'  dialysed  iron,  which  the  authors  have  im- 
ported and  had  ample  opportunity  for  comparison.  They  found 
that  it  can  be  produced  for  about  one-half  the  cost  of  the  imported. 

The  manner  of  taking  the  pure  concentrated  dialysed  iron  is 
generally  in  drops,  ranging  from  15  to  50  daily,  in  divided  doses, 
on  sugar  or  in  sugar  and  water ;  suitable  vehicles  can  be  used  for 
administration  without  fear  of  decomposition.  Being  without  taste 
and  odour,  compatible  with  syrup  and  alcohol,  and  communicating 
no  taste  to  any  suitable  vehicle,  it  is  easy  to  construct  formulae  for 
elixir,  syrup,  etc. ;  a  glycerite  is  stated  to  be  an  excellent  preparation, 

Dialysed  Iron.  J.  M.  Maisch.  (Amer.  Joum.  Pharm.,  1877,  342.) 
Dialysed  iron,  which  will  doubtless  become  one  of  the  most  valuable 
ferruginous  medicinal  agents,  has  been  recently  introduced  into 
the  United  States,  under  various  names.  Some  claiming  it  to  be  a 
solution  of  oxide  of  iron  in  water,  it  was,  and  is  still  frequently 
called  in  Europe,  ferrum  oxydatum  dialysatum ;  but  like  the  very 
simi'ar  preparation,  ferrum  oxydatum  saccharaticm,  which  has  been 
made  oflicinal  in  several  European  pharmacopoeias  (Amer.  Journ. 


13(5  YEAR-BOOK    OF    PHARMACY. 

Pharm.,  1873,  p.  161 ;  1874,  p.  559),  it  is  nothing  more  nor  less 
than  a  very  basic  oxjcliloride  of  iron.  To  prevent  erroneous  con- 
ceptions concerning  its  composition  gaining  a  foothold,  a  brief  review 
of  the  earlier  literature  on  the  subject  will  not  be  out  of  place. 

The  first  paper  on  this  subject  deserving  notice  is  one  by  John 
M.  Ordway,  entitled  "  Examination  of  the  Soluble  Basic  Sesquisalts," 
which  was  published  in  the  American  Journal  of  Science  and  Arts, 
2nd  series,  xxvi.,  197  (1858),  and  in  which  the  following  language 
is  used :  "  Time  is  a  very  important  element  in  the  production  of 
the  highly  basic  compounds.  One  may  easily  be  deceived  as  to  when 
the  hydrate  ceases  to  be  dissolved,  and  may  set  down  as  opaque 
that  which  by  longer  digestion  becomes  quite  transparent.  By 
successive  steps  we  get  pretty  easily  as  far  as  Fe.^  CI,;.  11  Fe,  O3, 
and  in  the  course  of  several  weeks  I  have  gone  as  high  as 
Fe,  Clg.  23  Fes  Os-" 

The  next  important  paper  is  by  Bechamp  (1859),  published  in 
Annates  de  Chimie  et  de  Physique,  3rd  series,  Ivii.,  296,  which  in  the 
main  coiToborates  the  statements  of  Ordway,  but  gives  the  most 
basic  compound  obtained  Feo  Clg.  20  Feg  O3.  In  both  cases  the 
solutions  of  the  normal  salt  were  digested  with  ferric  hydrate. 

Th.  Graham's  celebrated  essay  on  the  diffusion  of  liquids  (Phil. 
Trans.,  1861,  183)  announces  the  following  results  : — "  If  recently 
precipitated  ferric- hydrate  or  carbonate  of  ammonium  is  added  to 
an  aqueous  solution  of  ferric  chloride,  as  long  as  the  precipitates  are 
redissolved,  and  if  the  dark  red  solution  thus  obtained,  containing 
from  4  to  5  per  cent,  of  solid  matter,  is  subjected  to  dialysis,  mainly 
muriatic  acid  will  pass  through  the  septum,  upon  which,  after  19 
days,  remains  a  red  liquid  containing  for  98'5  parts  of  oxide  1*5  part 
of  muriatic  acid.  It  remains  liquid  for  20  days  and  then  gelatinizes, 
separating  ferric  hydrate.  A  similar  solution  of  colloidal  ferric 
hydrate  may  be  obtained  by  dialysis  of  ferric  acetate,  and  contains 
6  parts  of  acetic  acid  to  94  parts  of  ferric  oxide." 

Calculating  Graham's  results  as  an  oxychloride,  the  formula 
Fe,  Clg.  95  Fco  O3  would  be  obtained,  which  seems  to  be  hardly 
probable.  At  the  same  time,  it  must  be  remembered  that  none  of 
the  so-called  soluble  oxide  of  iron  has  as  yet  been  obtained  free 
from  acid.  Graham's  figures  are  the  lowest  thus  far  observed,  and 
the  solution  was  not  permanent,  but  gelatinized  spontaneously.  It 
must  therefore  be  granted  that  any  permanent  solution  of  so-called 
soluble  oxide  of  iron  must  contain  notable  quantities  of  acid ;  and 
within  the  past  year  such  has  been  proved  by  Hager  to  be  the  case 
with  several  Eui-opean  preparations  sold  as  oxide  of  iron. 


PHARMACEUTICAL   CHEMISTEY.  137 

The  behaviour  of  the  solutions  is  quite  curious  and  apt  to  mislead, 
unless  care  be  taken  to  arrive  at  correct  results.  They  will  retain 
their  clearness  on  boiling,  are  miscible  with  alcohol,  glycerin,  syrup, 
etc.,  but  readily  yield  precipitates  on  the  addition  of  acids  not  in  ex- 
cess, or  of  saline  solutions,  the  precipitates  disappearing  again  on 
dilutmg  with  distilled  water.  Tannin  added  in  small  quantities 
darkens  the  solution  somewhat,  and  on  filtering  leaves  but  little 
matter  in  the  funnel  ;  on  using  a  stronger  solution  of  tannin  a  well 
diffused  gelatinous  precipitate  takes  place,  having  a  deep  brown,  but 
not  a  black  colour,  and  the  filtrate  is  colourless.  Solution  of  nitrate 
of  silver  added  in  small  quantity  does  not  disturb  the  transparency 
of  the  liquid  ;  on  adding  more  of  the  former  a  gelatinous  hroivn  pre- 
cipitate takes  place,  and  the  colourless  filtrate  is  free  from  iron,  but 
the  addition  of  distilled  water  causes  the  precipitate  to  dissolve 
again.  Apparently,  therefore,  the  solution  is  free  from  chloride ; 
but  on  adding  first  a  .slight  excess  of  ammonia,  filtering  from  the 
ferric  hydrate,  acidulating  with  nitric  acid,  and  then  testing  with 
nitrate  of  silver,  a  white  precipitate  of  chloride  of  silver  is  formed. 
All  these  reactions  as  well  as  the  slight  astringent,  not  inky  taste, 
and  the  intense  brown-red  colour  have  been  observed  by  the  investi- 
gators named  above,  and  they  characterize  also  the  commercial 
products.  A  sample  recently  examined  by  the  writer,  and  said  to 
contain  no,  or  only  traces  of,  chlorine,  yielded  when  treated  as  above 
abundant  evidence  of  its  presence. 

Physicians  and  pharmacists  should  therefore  bear  in  mind  that 
there  is  no  soluhle  oxide  of  iron;  but  what  is  sold  as  such,  be  it  im- 
ported or  made  in  this  country,  is  very  basic  oxy chloride  of  iron. 
This  being  the  case,  the  question  naturally  presents  itself,  whether 
such  a  solution  cannot  be  obtained  by  saturating  a  solution  of  ferric 
chloride  with  hydrate  of  iron  ?  That  question  is  easily  answered  if 
the  behaviour  of  saline  solutions  is  taken  into  consideration  and  the 
fact  is  remembered  that,  when  solutions  of  ferric  salts  are  precipi- 
tated by  alkalies,  the  ferric  hydrate  will  invariably  retain  small 
quantities  of  the  precipitant,  which  cannot  be  removed  by  washing 
Avith  water.  These  saline  impurities,  minute  as  they  may  be,  are 
sufficient  to  prevent  the  formation  of  the  very  basic  oxychloride  ;  or 
if  formed  it  becomes  insoluble  in  the  liquid,  and  nothing  but  dialysis 
or  considerable  dilution  with  distilled  water  can  dissolve  it  again. 
To  obtain  it  of  the  maximum  strength  indicated  by  Graham  (5  per 
cent.)  and  also  adopted  by  the  Phai'maceutical  Society  of  Paris, 
dialysis  appears  to  be  unavoidable. 

As  to  the  advantage  of  the  dialysed  over  the  oxychloride  made  by 


138  TEAR-BOOK   OP    PHARMACY. 

saturation  -vrith  hydrate  of  iron,  that  is  best  ascertained  by  com- 
paring tlieir  taste,  which  in  the  former  is  scarcely  astringent,  while 
that  of  the  latter  is  distinctly  ferruginous.  A  preparation  imported 
from  Germany,  called  ferrum  oxydatum  dialysatum,  which  was 
received  and  examined  by  the  author,  appeared  to  have  been  made 
by  saturation  alone,  or  by  incomplete  dialysis  ;  for  its  reaction  is  dis- 
tinctly acid  and  its  taste  quite  styptic.  Some  French  preparations, 
sold  by  the  same  name,  were  found  to  be  superior  to  the  German  in 
both  respects ;  but  one  yielded  only  3"3  per  cent,  of  solid  matter, 
another  less  than  half  that  quantity.  A  5  per  cent,  solution  of 
dialysed  iron  should  yield  3  grains  of  dry  residue  when  GO  grains 
of  it  are  carefully  evaporated  to  complete  dryness. 

The  characteristics  of  a  5  per  cent,  solution  of  dialysed  iron  may 
be  stated  to  be — 

1.  The  deep  brown-red  colour,  which  in  thin  layers  is  perfectly 
transparent. 

2.  The  freedom  from  odour  and  taste,  it  being  merely  faintly 
astringent  to  the  palate. 

3.  The  absence  of  even  slight  acid  reaction  to  test  paper ;  and 

4.  The  behaviour  to  tannin  and  to  saline  solutions  (even  spring 
water),  as  stated  above. 

It  is  best  given  by  itself  upon  sugar,  or  mixed  with  some  simple 
syrup  which  is  free  from  acid.  It  should  be  mentioned  yet  that  the 
same  preparation  has  made  its  appearance  in  Austria  as  catalytic 
iron. 

Note  upon  a  Reaction  of  Emetine.  F.  B.  Power.  (Amer.  Journ. 
Pharm.,  1877,  391.)  A  solution  of  chlorinated  lime  produces  with 
emetine  a  bright  orange  or  lemon  yellow  coloration,  and  is  con- 
veniently employed  by  touching  a  trace  of  the  alkaloid^  upon  a  porce- 
lain plate  with  a  drop  of  the  alkaline  solution :  the  reaction  being 
much  favoured  by  the  addition  of  a  drop  of  acetic  or  other  weak 
acid,  to  insure  the  liberation  of  the  hypochlorous  acid,  upon  which 
the  reaction  apparently  depends,  as  chlorine  is  incapable  of  produc- 
ing the  coloration,  which  is  permanent  and  maybe  quite  indefinitely 
retained. 

A  few  drops  of  a  solution  of  one  part  of  emetine,  in  1000  parts  of 
water,  when  evaporated  to  dryness  and  brought  in  contact  with  a 
drop  of  the  alkaline  solution,  readily  produces  the  coloration ;  and 
with  a  solution  containing  one  part  of  the  alkaloid  in  5000  parts  of 
water,  the  yellow  coloration  is  still  perceptible. 

In  view  of  the  isolation  of  the  alkaloid  when  mixed  with  compli- 
cated organic  substances,  it  must  be  remembered  that  it  is  not  ab- 


PHARMACEUTICAL    CHEMISTRY.  139 

sorbed  from  acid,  but  very  readily  from  alkaline  solutions  by  amylic 
alcohol,  chloroform,  benzol,  and  petroleum  benzin. 

The  reaction  may  also  be  employed  as  a  means  of  testing  the 
value  of  various  species  of  ipecacuanha.  If  a  gram  of  the  root  of 
GeplueUs  ipecacuanha  in  fine  powder,  or  the  cortical  portion  therein 
contained,  be  treated  according  to  the  process  described  by  Prof. 
Fliickiger  for  the  isolation  of  emetine,  i.e.,  mixed  with  a  small 
amount  of  quicklime  and  a  few  drops  of  water,  the  mixture  allowed 
to  dry  upon  the  water  bath,  subsequently  exhausted  by  chloroform, 
and  the  filtrate  allowed  to  evaporate  in  a  capsule  containing  a  few 
drops  of  dilute  acetic  acid,  the  nearly  colourless  residue  thus  ob- 
tained affords  with  the  alkaline  solution  the  characteristic  color- 
ation. 

The  root  of  Richardsonia  scahra,  Lin.,  or  undulated  ipecacuanha, 
which  is  occasionally  quoted  as  a  source  of  emetine,  when  similarly 
treated  does  not  produce  this  reaction,  a  fact  which  may  confirm 
the  supposition  already  entertained,  that  this  root  is  destitute  of 
alkaloid. 

Detection  of  Sugar  in  Glycerin.  A.  Schillberg.  (Pharmaceut. 
Centralhalle,  1877,  115.)  Pure  glycerin  when  boiled  with  an  equal 
volume  of  hydrochloric  acid  (containing  about  25  per  cent,  of  HCl) 
remains  colourless;  but  if  the  least  admixture  of  sugar  be  present,  a 
yellow  or  yellowish  red  coloration  is  produced.  The  glycerin  takes 
no  part  in  the  reaction,  as  the  same  coloration  is  produced  on  heat- 
ing a  weak  aqueous  solution  of  sugar  with  the  acid.  Accoi'ding  to 
the  author  this  reaction  is  the  same  which  W.  W.  Stoddart  con- 
sidered to  be  duQ  to  the  colouring  matter  of  saffron  (see  Year-Booh 
of  Pharmacy^  1876,  494). 

Cochineal  Testing.  J.  M.  Merrick.  {Zeitschr.  filr  Analyt.-Ghem., 
XV.,  41)3.)  In  determining  the  value  of  a  sample  of  cochineal  by 
titration  of  its  colouring  matter  with  potassium  permanganate,  as 
previously  described  by  the  author  (^Zeitschr.  fur  Analyt.-Ghem.,  xi., 
230),  it  should  be  understood  that  there  is  a  marked  difference  be- 
tween black  and  silver  cochineal  in  their  behaviour  with  the  reagent 
named.  If  permanganate  be  added  to  solutions  of  the  colouring 
matter  of  the  two  kinds  until  both  show  the  same  yellow  coloiir, 
no  farther  change  will  be  observed  for  some  time  in  either  ;  but  if 
the  mixtures  be  allowed  to  stand  for  8  to  12  hours,  that  obtained 
from  the  black  cochineal  will  aj^pear  deep  red,  whereas  the  other 
remains  still  unaltered.  To  avoid  errors  it  is  necessary,  therefore, 
to  keep  standard  samples  of  both  kinds  of  cochineal,  so  that  the 
sample  tested  may  be  compared  with  a  sample  of  its  own  kind. 


14-0  YEAK-BOOK    OF    PHARMACY. 

Sclerotic  Acid.  The  Preparation  and  Properties  of  Sclerotic 
Acid.  Prof.  G.  Dragendorff  and  M.  Podwissotzky.  {Neio 
Bemedies,  from  Pharm.  Zeit.  fur  liussland,  1877,  No.  5.)  In  a 
previous  report  on  the  constituents  of  ergot  (a  summary  of  which 
will  be  found  in  the  Year-Book  of  Pho.rmacij,  187G,  p.  2-i7),  the 
authors  announced  the  isolation  of  a  proximate  principle  of  an  acid 
character,  possessing  in  a  high  degree  the  physiological  properties  of 
the  drug.  In  a  more  detailed  report  of  their  researches  subsequently 
published,  they  furnish  a  full  account  of  their  method  of  preparing 
this  principle,  which  they  have  named  "  sclerotic  acid." 

Very  finely  powdered  ergot  is  exhausted  with  distilled  water,  the 
solution  concentrated  in  vacuo,  and  the  residuary  liquid  mixed  with 
an  equal  volume  of  95  per  cent,  alcohol.  This  causes  the  precipita- 
tion of  a  peculiar  slimy  substance,  scleromucin,  together  with  a 
portion  of  the  salts  and  the  greater  part  of  the  suspended  fatty 
matter.  The  mixture  having  been  allowed  to  stand  on  ice  for 
twenty-four  or  forty-eight  hours,  it  is  filtered  and  the  filtrate  mixed 
with  a  f  uz'ther  quantity  of  95  per  cent,  alcohol,  sufficient  to  precipi- 
tate all  the  sclerotic  acid  in  combination  with  the  bases  (chiefly  as 
calcium  sclerotate).  The  separation  of  the  precipitate  is  promoted 
as  before  by  placing  the  mixture  ou  ice  for  some  days.  This  causes 
the  deposited  mass,  which  has  a  brownish  colour,  to  adhere  firmly 
to  the  walls  of -the  vessel,  so  as  to  permit  the  supernatant  liquid  to 
be  easily  poured  ofi".  The  precipitate  is  kneaded  with  alcohol  of  80 
per  cent.,  and  immediately  thereafter  dissolved  in  a  sulficieut  quan- 
tity of  40  per  cent,  alcohol,  when  the  remainder  of  the  scleromucin 
and  another  larger  portion  of  the  foreign  salts  are  left  behind.  The 
filtered  liquid  is  now  mixed  with  absolute  alcohol,  whereby  sclerotic 
acid  is  precipitated  in  conjunction  with  certain  bases  and  other  sub- 
stances. The  impure  product,  when  carefully  dried  over  sulj^huric 
acid,  was  found  on  analysis  to  contain  8"5  per  cent,  of  potassium, 
about  036  per  cent,  calcium,  4"3  per  cent,  sodium,  2' 74  per  cent, 
phosphoric  and  3'4  per  cent,  silicic  acid  ;  or  altogethei",  12'9  per  cent- 
of  ash. 

The  greater  part  of  these  admixtures  may  be  removed  and  the 
sclerotic  acid  obtained  free,  by  adding,  before  the  final  precipitation 
with  absolute  alcohol,  a  considerable  quantity  of  hydrochloric  acid 
(for  every  100  c.c.  of  solution,  5-6  grams  of  the  acid,  sp.  gr.  I'lOO), 
allowing  to  stand  at  ordinary  temperature  for  a  few  hours,  and  then 
proceeding  to  precipitate.  In  this  manner  the  amount  of  ash  may 
be  brought  down  to  3  per  cent.,  and  by  repeated  solution,  addition  of 
acid,  and  precipitation,  it  may  further  be  reduced  to  less  than  2  per 


PHARMACEUTICAL    CHE3IESTRY.  141 

cent,  or  3  per  cent.  A  more  complete  purification  is  difficult  and 
hazardou.s,  becaiise  every  addition  of  hydrochloric  acid  causes  the 
decomposition  of  a  small  quantity  of  the  sclerotic  acid,  while  at  the 
same  time  a  portion  of  the  latter  is  lost  by  remaining  in  solution. 

The  resulting  product,  although  not  chemically  pure,  is  neverthe- 
less, so  to  say,  physiologically  pure,  as  it  always  produces  constant 
and  identical  results,  no  matter  from  what  sample  of  (good)  ergot 
it  was  obtained. 

Sclerotic  acid  is  entirely  odourless  and  tasteless.  In  aqueous 
solution  it  has  a  faint  acid  reaction,  and  decomposes  calcium  car 
bonate  slowly,  even  on  warming.  Boiling  nitric  acid  of  1"200  sp. 
gr.  produces  a  little  picric  and  oxalic  acid,  and  a  new  substance, 
which  assumes  a  bright  yellow  colour  on  adding  ammonia  or  other 
alkalies.  More  concentrated  nitric  acid  converts  it  into  picric, 
oxalic,  mucic,  tartaric,  and  aposorbic  acids.  It  is  not  a  glucoside  ; 
nor  does  it  lose  its  effectiveness,  on  the  addition  of  dilute  sulphuric 
or  hydrochloric  acids  ;  on  the  contrary,  the  latter  appears  to  inten- 
sify its  effects.  Boiling  alcohol,  in  presence  of  sulphuric  acid,  extracts 
it  from  ergot  in  small  quantities,  cold  alcohol  not  at  all.  It  is  there- 
fore possible  to  abstract  by  means  of  cold  alcohol  and  sulphuric  acid 
a  portion  of  the  colouring  matter  from  ergot,  before  extracting  the 
sclerotic  acid  with  water.  But,  unfortunately,  the  aqueous  solutions 
(which  carry  with  them  a  portion  of  the  alcohol  and  sulphuric  acid) 
spurt  or  bump  so  energetically  during  the  distillation,  that  this 
modification  of  the  process  becomes  unadvisable. 

It  might  be  supposed  that  sclerotic  acid  is  not  an  acid,  but  an 
alkaloid,  as  it  yields  with  phosphomolybdic  acid  a  yellow,  and  with 
tannin  an  almost  colourless,  precipitate.  But  other  alkaloidal  preci- 
pitants  are  without  action  upon  it,  and  only  lead  acetate  with 
ammonia  produces  a  strong  flocculent  precipitate. 

When  properly  purified,  sclerotic  acid  is  hygroscopic  but  not  deli- 
quescent, which  circumstance  distinguishes  it  advantageously  from 
the  commercial  purified  extracts  of  ergot.  It  is  found  in  these  in 
greater  or  lesser  quantity  according  as  a  weaker  or  a  stronger 
alcohol  was  employed  in  exhausting  the  ergot.  A  few  commercial 
extracts  were  found  to  be  very  deficient.  In  Bonjean's  and  Wer- 
nich's  prepai-ations  and  in  Wigger's  osmazom  it  exists  in  consider- 
able quantity,  while  scleromucin  is  almost  entirely  absent,  as  is  the 
case  in  all  alcoholic  extracts  of  ergot.  In  ZweifFel's  preparation  the 
acid  occurs  ina  tolerably  pui'e  state,  in  a  less  pure  condition  in  Buch- 
heim's.  In  alcoholic  tinctures  of  ergot,  and  in  Wigger's  ergotin,  it 
is  only  present  in  traces  or  is  entirely  absent. 


142  YEAR-BOOK    OF    PHARMACY. 

Good  ergot  contains  about  4  to  45  per  cent,  of  the  acid,  although, 
samples  are  met  with  which  contain  scarcely  1*5  to  2  per  cent. 

The  Alkaloids  in  Agaricus  Muscarius.  E.  Harnack.  (Zeitschr. 
des  oesterr.  Apotli.  Ver.,  from  Chem.  Centralhlatt,  vii.,  560.)  Koppe 
and  Schmiedeberg  have  isolated  from  this  fungus  a  poisonous 
alkaloid,  to  which  they  have  given  the  name  "  muscarine." 

The  author  has  obtained  a  second  alkaloid,  which,  however,  is 
devoid  of  poisonous  properties,  by  treating  the  aqueous  extract  of 
the  fungus  with  water  acidified  with  hydrochloric  acid,  evaporating 
to  the  point  of  crystallization,  and  pressing  the  crystalline  mass  thus 
obtained  between  filtering  paper,  which  absorbs  the  very  hygroscopic 
salt  of  muscarine,  leaving  the  hydrochlorate  of  the  second  alkaloid. 

The  formula  of  muscarine  is  Cj  H^g  N  Oo,  that  of  amanitine,  the 
second  alkaloid  just  referred  to,  C5  H^g  N  0,  which  is  the  same  as 
that  of  choline.  Amanitine,  however,  is  not  identical  with  choline 
as  by  oxidation  by  chromic  acid  it  does  not  yield  betaine,  but  is  par- 
tially converted  into  muscarine. 

Chemistry  of  the  Barks  of  the  Oak,  WUlovr,  and  Elm.  E. 
Johansen.  (Juudi.  GJtem.  Soc,  from  Arcliiv  der  Pliarmacie  [3], 
ix.,  210-248.)  The  investigation  was  undertaken  with  the  view  of 
ascertaining  the  nature  of  the  different  tannin-like  substances  con- 
tained in  the  barks  of  the  oak,  willow,  and  elm,  and  it  was  hoped, 
by  isolating  these  and  carefully  examining  their  properties  and  the 
natuie  of  their  principal  compounds,  to  ascertain  whether  they  were 
analogous  or  even  identical.  By  a  long  and  elaborate  process,  the 
different  tannins  were  separated  from  the  three  barks  in  something 
like  a  pure  state. 

Oah  Tannin  is  a  red-brown,  amorphous,  glistening  body,  easily 
soluble  in  alcohol,  slightly  soluble  in  ether,  and  forms  an  imper- 
fectly clear  solution  in  water.  In  its  behaviour  to  litmus  paper, 
metallic  salts,  and  alkaloids,  it  is  completely  analogous  to  gallotan- 
nic  acid.  Dried  at  110°  it  lost  848  percent,  of  water.  On  analysis 
it  gave  64"61  per  cent,  of  carbon,  5"32  per  cent,  of  hydrogen,  and 
40'07  per  cent,  of  oxygen,  agreeing  approximately  with  Wagner's 
formula,  CuHj^Og,  which  requires  5.385  per  cent,  of  carbon  and 
5'13  per  cent,  of  hydrogen.  It  contains  also  0'77  per  cent,  of  nitro- 
gen and  0"13  per  cent,  of  ash. 

Wdloio  Tannin  consists  of  a  brown-red  amorphous  body,  with  a 
slightly  astringent  taste;  easily  soluble  in  alchohol,  slightly  soluble 
in  ether,  and  forming  a  thick  solution  with  water.  With  ferric  salts 
it  gives  a  deep  black  colour,  turned  violet-red  by  alkalies.  It  pre- 
f.ipitates  murcuric   nitrate  and  chloride,  and   zinc  and  copper  sul- 


PHARMACEUTICAL   CHEMISTRY.  143 

phates,  as  well  as  albumen,  starch,  and  alkaloids.  At  120°  the 
■willow  tannin  lost  lO'lO  per  cent,  of  water,  and  on  analysis  gave 
61'13  per  cent,  of  carbon,  4"78  per  cent,  of  hydrogen,  and  4409  per 
cent,  of  oxygen.  It  contains  also  1'88  per  cent,  of  nitrogen  and  1'63 
per  cent,  of  ash.  Another  specimen,  prepared  in  a  different  manner, 
though  possessing  the  same  reactions  as  the  last,  contained  51 '26 
per  cent,  of  carbon  and  5*99  per  cent,  of  hydrogen,  besides  having 
independently  0'44  per  cent,  of  nitrogen  and  1'42  per  cent,  of  ash. 

Elm  Tannin. — In  appearance  and  solubility  this  variety  resembles 
oak  tannin.  With  ferric  chloride,  it  gives  a  dirty  green  precipitate, 
turned  violet-red  by  sodium  hydrate.  With  ferrous  sulphate  it  gives 
a  pure  green  precipitate.  It  precipitates  lead  and  copper  acetates, 
and  zinc  sulphate  after  some  time.  With  zinc  chloride,  mercuric 
nitrate,  calcium  acetate,  etc.,  it  gave  the  usual  reactions.  At  110° 
elm  tannin  loses  3"32  per  cent,  of  water,  and,  on  analysis,  gives  44'54 
per  cent,  of  carbon,  4' 72  per  cent,  of  hydrogen,  and  50' 71  per  cent, 
of  oxygen,  besides  containing  1'21  per  cent,  of  ash. 

The  salts  of  these  three  tannin  acids  (quercitannic,  salitannic,  and 
ulmotannic)  were  next  examined. 

Lead  Salts. — Quercitannate  of  lead  is  a  chocolate-brown,  amor- 
phous mass,  slightly  soluble  in  water,  insoluble  in  alcohol  or  ether. 
On  heating  it  to  110°  it  lost  9"66  per  cent,  of  water  ;  and  on  analy- 
sis it  gave  22'85  per  cent,  of  carbon,  1'47  per  cent,  of  hydrogen,  9"14 
per  cent,  of  oxygen,  and  36" 54  per  cent,  of  lead  oxide.  The  salitan- 
nate  of  lead  resembled  the  last  body,  and  on  drying  at  120°  lost  4'50 
per  cent,  of  water,  and  on  analysis  gave  22 •53  per  cent,  of  carbon, 
1'35  per  cent,  of  hydrogen,  and  5328  per  cent,  of  lead  oxide.  By 
fractionally  precipitating  with  a  lead  salt,  both  these  acids  gave  salts 
of  varying  constitution.  Ulmotannate  of  lead  was  greyer  than  the 
last  body,  and  on  analysis  gave  21"36  per  cent,  of  carbon,  1'51  per 
cent,  of  hydrogen,  10'32  per  cent,  of  oxygen,  and  66"81  per  cent,  of 
lead  oxide. 

Copper  Salts. — Quercitannate  of  copper  is  a  brown  substance,  in- 
soluble in  alcohol  and  ether,  and  sparingly  soluble  in  water.  At  110° 
it  lost  12'23  per  cent,  of  moisture,  and  on  analysis  gave  3999  per 
cent,  of  carbon,  2'38  per  cent,  of  hydrogen,  28'14  per  cent,  of  oxygen, 
and  29  49  per  cent,  of  copper  oxide.  Salitannate  of  copper  forms 
a  dark  reddish  brown  salt,  which  lost  at  120°  12"4  per  cent,  of 
moisture,  and  on  analysis  gave  39"36  per  cent,  of  carbon,  235  per 
cent,  of  hydrogen,  27'83  per  cent,  of  oxygen,  and  3046  per  cent,  of 
copper  oxide.  Ulmotannate  of  copper  is  chocolate-brown,  and  after 
drying  at  110°  gave  3968  per  cent,  of  carbon,  1-93  per  cent,  of 


144  TEAR-BOOK   OF    PHARMACY. 

hydrogen,  17'98  per  cent,  of  oxygen,  and  40"41  per  cent,  of  copper 
•oxide. 

Tin  Salts. — Quercitannate  of  tin  is  a  greenish  brown  substance, 
insoluble  in  alcohol  and  ether,  and  only  sparingly  soluble  in  water. 
At  110°  it  loses  5'98  per  cent,  of  moisture,  and  on  analysis  gave 
30'32  per  cent,  of  carbon,  2o6  per  cent,  of  hydrogen,  20G9  per 
cent,  of  oxygen,  and  40'43  per  cent,  of  stannous  oxide.  The  fornuila 
C3oHngOj3.  3  Sn  0  agrees  fairly  with  these  numbers.  Salitannate 
of  tin  is  a  chocolate-coloured  body,  which  loses  7' 18  per  cent,  of 
moisture  at  120°,  and  on  analysis  gives  3o"17  per  cent,  of  carbon, 
2"79  per  cent,  of  hydrogen,  1505  per  cent,  of  oxygen,  and  4G"50  per 
cent,  of  stannous  oxide.  Ulraotannate  of  tin  on  drying  at  110°  gave 
38"99  per  cent,  of  carbon,  2"40  per  cent,  of  hydrogen,  13"66  per  cent, 
of  oxygen,  and  44*95  per  cent,  of  stannous  oxide. 

When  these  different  tannins  were  acted  on  by  dilute  acids  in  the 
usual  manner,  as  Grabowski  has  already  shown,  the  oak  tannin 
yields  an  easily  decomposed  saccharide  and  a  crystalline  body.  The 
amount  of  these  bodies  obtained  varies  with  the  strength  of  acid 
employed.  On  purification  the  saccharide  is  obtained  as  a  brown 
substance,  forming  a  dark  brown  bitter  syrup.  Similar  bodies  were 
obtained  from  the  willow  tannin.  On  analysis  the  saccharide  ob- 
tained from  the  willow  tannin  gave  36*94  per  cent,  of  carbon,  519 
per  cent,  of  hydrogen,  and  5787  per  cent,  of  oxygen.  Elm  tannin, 
on  the  contrary,  yields  no  crystalline  body,  but  only  a  saccharide 
resembling  in  every  respect  the  last. 

On  fusing  with  potassium  hydrate,  the  oak  tannin  yields,  amongst 
other  products,  butyric  acid  amongst  the  volatile  products,  and 
protocatechuic  acid  from  the  residue.  Willow  tannin,  similarly 
treated,  yielded  acetic  and  butyric  acid  amongst  the  volatile  pro- 
ducts, whilst  the  residue  in  the  retort  contained  a  body  whose 
identity  could  not  be  satisfactorily  made  out.  Elm  tannin,  treated 
in  the  same  manner,  yielded  acetic  and  butyric  acids  among  the 
volatile  products,  and  oxyphenic  acid  in  the  residue. 

Artificial  OU  of  Mustard.  Dr.  E.  Mylius.  (Archiv  der  Pharm., 
[3],  X.,  207.)  Some  time  ago  Dr.  Schacht  stated  at  a  meeting  of 
Berlin  pharmacists  that  owing  to  the  identity  of  artificially  prepared 
oil  of  black  mustard  with  the  genuine  oil,  the  former  might  with 
perfect  propriety  be  substituted  for  the  latter  in  pharmacy.  Having 
observed  a  decided  difference  in  the  odour  of  the  two  preparations,  the 
author  submitted  a  quantity  of  the  best  artificial  oil  he  could  obtain 
to  fractional  distillation,  and  a  thoi'ough  chemical  examination  of 
the  fractions.     He  found  1000  parts  of  the  oil  to  contain — 


PHARMACEUTICAL    CHEMISTRY.  145 

Allyl  Sulphocyanide      ....  922    pajts> 
Carbon  Bisulphide         ....  8       ,, 

Hydrocyanic  Acid  ....  0*2    ,, 

Polysulphides  (chiefly  allyl  trisiilphide)  40       ,, 

Bodies  not  volatile  without  decomposition, 
containing  both  nitrogen  and  sulphur  30       ,, 

From  these  results  the  author  draws  the  conckision  that  Until  a 
satisfactory  and  inexpensive  method  of  purifying  the  artiBcial  oil  of 
mustard,  as  met  with  in  commerce,  can  be  devised,  this  oil  ought  not 
to  take  the  place  of  the  genuine  product  in  pharmacy.  The  oil  ex- 
amined by  him  was  probably  the  nnpurified  product  of  the  diy 
distillation  of  a  mixture  of  allyl-sulphate  and  sulphocyanide  of  potas- 
sium. An  oil  prepared  from  iodide  of  allyl  and  sulphocyanide  of 
potassium  would  be  more  expensive  than  the  genuine  article. 

Determination  of  Potassium  as  Potassium  Platinochloride  in 
Presence  of  Chlorides  of  the  Metals  of  the  Alkaline  Earths.  Prof. 
R.  Fresenius.  (^Zeitschr.  fur  Analyt.-Ghem.,  xvi.,  63-65;  Jourri. 
Ghem.  Soc,  1877,  218.)  This  method,  at  the  commencement,  does 
not  differ  from  that  usually  employed.  The  concentrated  solution 
is  treated  in  a  small  porcelain  dish,  -with  excess  of  pure  platinum 
chloride  in  excess,  evaporated  on  a  water  bath  (below  100°)  to  a 
syrupy  consistence,  carefully  mixed  with  alcohol  of  80  per  cent., 
and  left  a  short  time  with  frequent  stirring.  By  this  means  the 
platino-potassium  chloride,  insoluble  in  alcohol,  is  separated  from 
the  sodium  salt,  which  goes  into  solution. 

At  this  stage  the  method  begins  to  differ  from  the  usual  one. 
The  alcoholic  solution  is  poured  through  a  small  filter,  and  the  re- 
sidue in  the  dish  treated  with  alcohol,  till  the  potassium  salt  appears 
pure.  This  is  then  collected  on  the  filter  and  washed  thoroughly 
with  alcohol  of  the  same  strength.  The  filter  is  then  dried,  to 
ensure  the  complete  expulsion  of  the  alcohol.  If  the  quantity  of 
the  salt  thus  collected  be  large,  it  may  be  .separated  as  much  as 
possible  from  the  filter-jmper,  from  which  the  remaining  salt  is 
removed  by  boiling  water ;  the  solution  is  then  evaporated  to  dry- 
ness in  a  small  platinum  dish.  The  main  bulk  is  then  added,  the 
whole  dried  at  130°,  and  weighed.  If  the  quantity  is  small,  the 
precipitate  may  be  wholly  washed  off  the  filter  into  the  platinum 
dish,  evaporated,  and  weighed  as  above. 

To  ascertain  whether  the  weighed  potassio-platinum  salt  is  pure, 
treat  it  with  repeated  quantities  of  hot  water,  leave  it  to  settle,  and 
decant  the  solution  into  a  dish.  A  little  platinum  chloride  is  then 
added,  to   convert   any  sodium  chloride  into  the  platinum-sodium 

L 


146  YE,\.n-BOOK    OF    PHARJIACi*. 

salt,  the  solution  evaporated  as  above  almost  to  dryness,  and  mixed 
with  alcohol  of  80  per  cent.  The  deposited  potassium  salt  is  filtered 
off  and  washed  with  alcohol,  dried  on  the  filter,  and  washed  with 
boiling  water  iu  a  platinum  dish,  into  which  the  undissolved  bulk  of 
the  original  precipitate  is  brought.  The  whole  is  evaporated  to  dry- 
ness, dried  at  130^,  and  weighed.  Should  any  alteration  in  weight 
have  taken  place,  the  previous  precipitate  was  impure,  and  the 
present  weight  may  be  regarded  as  the  right  one.  Pure  plati  no- 
potassium  chloride  must  dissolve  entirely  in  boiling  water. 

As  regards  the  accui-acy  of  the  above  method  in  presence  of  other 
alkaline  salts,  the  following  results  are  insti'uctive.  In  a  solution 
of  potassium  chloride,  the  potassium  was  determined  as  above,  at 
first  in  the  normal  solution,  then  with  addition  of  chlorides  of 
barium,  strontium,  calcium,  and  magnesium  respectively.  The  re- 
sults show  that  the  method  maintains  its  accuracy  in  presence  of 
the  chlorides  of  any  of  the  alkali-metals  ;  but  that  when  magnesium, 
barium,  and  strontium  respectively  are  present,  the  results  were 
very  slightly  in  excess.  To  obtain  perfectly  accurate  results  the 
process  recommended  above  should  be  strictly  adhered  to. 

Note  on  the  Volumetric  Estimation  of  Phosphoric  and  Arsenic 
Acids  by  Uranium.  G.  Briigelmanu.  (Fharin.  Centralhalle, 
1877,  12-i,  from  Zeitsclir.  fur  Analyi.-Ckem.)  The  author  suggests  the 
following  modification  of  the  uranium  process  generally  employed  : — 
The  aqueous  or  acid  solution  of  the  phosphate  or  arseniate  is  mixed 
with  a  quantity  of  solution  of  sodium  hydrate  just  suificient  to  im- 
part to  the  mixture  a  distinct  alkaline  reaction.  Acetic  acid  is  then 
added  in  excess,  and  the  titration  with  uranium  solution  carried 
out  in  the  usual  manner,  potassium  ferrocyauide  being  used  as  an 
indicator.  Xo  addition  of  sodium  or  ammonium  acetate  is  made 
before  the  titration.  In  this  way  only  a  very  small  quantity  of 
alkaline  acetate  is  contained  in  the  mixture,  and  the  smallest  excess 
of  uranium  will  be  readily  indicated  by  the  ferrocyauide,  whereas  iu 
the  presence  of  larger  quantities  of  acetate  the  sensitiveness  of  the 
reaction  is  considerably  diminished,  so  as  to  necessitate  the  correc- 
tion usually  made  in  this  titration.  The  author's  process  renders 
this  correction  superfluous. 

Detection  of  Artificial  Colouring  Matters  in  Wine.  A.  Dupre. 
(Analyst,  187G,  26.)  The  colouring  matter  of  pure  red  wine  does 
not  pass  through  the  dialyser.  The  dialysate  from  pure  wine  is 
therefore  colourless,  or  shows  but  a  slight  purplish  coloration,  such 
as  water  would  assume  on  the  addition  of  a  small  quantity  of  the 
the  wine.     A  yellow   ov    brownish   yellow    dialysate    indicates  an 


I 


PHARMACEUTICAL    CHEMISTRY,  147 

adulteration  with  logwood,  brazil  wood,  or  cochineal,  the  colouring 
matters  of  which  may  then  be  identified  by  the  chemical  and  optical 
tests  usually  employed  for  this  purpose.  The  ammoniacal  solution 
of  the  colouring  matter  of  cochineal  yields  thi'ee  well-marked  absorp- 
tion bands. 

Detection  of  Fuchsine  in  Wine.  The  following  methods  are  re- 
commended by  E.  Jacquemin  in  the  Gomi)tes  Rendus,  Ixsxiii.,  70: — 

1.  A  small  quantity  of  gun  cotton  is  heated  for  a  few  minutes  in 
10-20  c.c.  of  the  wine,  and  then  washed  with  water.  The  natui'e  of 
the  coloration  (if  any)  imparted  to  the  cotton  is  now  identified  by 
means  of  solution  of  ammonia,  which  decolorises  rosauiline  but 
turns  archil  violet. 

2.  100  c.c.  of  the  wine  are  boiled  to  expel  the  alcohol,  and  then 
boiled  for  some  time  with  white  Berlin  wool,  previously  moistened 
with  water.  The  colour  imparted  to  the  wool  by  fuchsine  is  re- 
tained after  washing,  and  may  be  distinguished  from  archil  by 
ammonia. 

3.  100-200  c.c.  of  the  wine  are  boiled  to  expel  the  alcohol,  then 
allowed  to  cool,  mixed  with  ammonia  in  excess,  and  shaken  with 
ether.  By  immersing  white  wool  in  the  ethereal  solution,  and 
evaporating  the  latter,  the  wool  acquires  the  characteristic  colour 
of  fuchsine. 

C.  Husson  (Ibid.,  199)  suggests  the  following  mode  of  testing  : — 

Place  a  few  c.c.  of  the  wine  in  a  phial  and  add  ammonia,  then 
immerse  a  piece  of  white  Berlin  wool  in  the  mixture,  withdraw  it 
after  it  is  well  soaked,  and  pour  upon  it  a  drop  of  dilute  acetic  acid. 
In  the  presence  of  fuchsine  the  wool  thus  acquires  a  red  tint. 

Pure  fuchsine  is  not  very  poisonous. 

The  method  of  estimating  the  arsenic  which  may  have  been  intro- 
duced with  the  fuchsine  into  the  wine,  depends  upon  the  fact  that 
if  arseniuretted  hydrogen  be  passed  into  a  solution  of  iodine  in  beti- 
zine,  the  colour  of  that  solution  is  rapidly  destroyed,  whilst  it  is  not 
affected  by  pure  hydrogen. 

It  was  found  by  experiment  that  O'Ol  gram  of  arsenic  in  the  form 
of  arseniuretted  hydrogen  was  decomposed  by  0*02  gram  of  iodine. 
The  process  is  to  be  practised  as  follows : — 

Having  decomposed  the  suspected  matter  by  the  ordinary  pro- 
cesses, so  as  to  obtain  the  arsenic  as  a  potash-salt,  this  is  dis- 
solved in  distilled  water,  and  the  solution  divided  into  two  parts  : 
one  is  reserved  for  qualitative  examination,  the  other  divided  into 
two.  in  one  of  which  the  arsenic  is  approximately  determined  by 
pouring  it  into  a  Marsh's  apparatus  which  is  evolving  pure  hydro- 


148  YEAR-BOOK    OF    PHAl.'MACY. 

gen,  aud  passing  the  gas  into  a  measured  quantity  of  a  standard 
solution  of  iodine  in  benzine,  and  as  this  is  decolorised,  gradually 
adding  more  from  a  burette  until  the  decolorisation  ceases.  In  the 
other  part  of  the  solution  the  quantity  of  arsenic  is  exactly  deter- 
mined by  pouring  it  into  a  Marsh's  apparatus  as  before,  and  allow- 
ing the  evolved  gas  to  pass  through  a  series  of  about  six  test-tubes, 
each  containing  a  known  amount  of  iodine  :  for  example,  in  the  1st 
0-01  gram;  2nd  and  3rd,  0-005  gram;  4th,  O'OOl  gram  ;  5th,  0-0005 
gram  ;  and  6th,  00001  gram;  but  these  quantities  maybe  varied  ac- 
cording to  the  indications  afforded  by  the  previous  experiment.  By 
noting  the  number  of  test-tubes  coloured,  the  exact  quantity  of 
arsenic  introduced  into  the  Marsh's  apparatus  can  be  ascertained. 

The  process  recommended  by  L.  Lamattena  (Ibid.,  564)  is  as 
follows  : — 

Fuchsiue  may  be  detected  by  mixing  100  grams  of  the  wine  with 
15  grams  of  coarsely  powdered  manganese  dioxide,  shaking  for  12  or 
15  minutes,  and  filtering  through  a  double  filter-paper.  If  the  wine 
is  pure  it  passes  through  colourless ;  if  adulterated,  some  artificial 
colouring  matter  has  been  used.  If  pure  peroxide  is  used,  this  pro- 
cess is  unexceptionable ;  but  if  the  manganese  contains  iron,  the 
acids  of  the  wine  dissolve  it,  and  it  forms  an  insoluble  lake  with  the 
colours  which  remain  on  the  filter.  If  in  this  case  the  residue  on 
the  filter  is  treated  with  alcohol,  the  fuchsine  dissolves,  aud  may  be 
immediately  recognised  by  adding  strong  acetic  acid  and  a  few  drops 
of  ammonia. 

Another  process  is  described  by  E.  Bouilhon  (Ibid.,  858)  : — 
500  c.c.  of  the  wine  are  placed  in  a  capsule,  raised  to  a  boil, 
and  evaporated  down  to  125  c.c. ;  the  capsule  is  then  withdrawn 
from  the  fire,  and  20  grams  crystalline  hydrate  of  baryta  are  added. 
The  mixture  is  agitated  to  facilitate  the  reaction,  allowed  to  cool, 
poui-ed  upon  a  filter,  and  the  precipitate  washed  with  distilled  water, 
so  as  to  obtain  in  all  125  c.c.  of  filti'ate.  It  is  then  necessary  to 
ascertain,  by  the  addition  of  a  few  crystals  of  hydrate  of  baryta  to 
the  filtered  liquid,  that  the  precipitation  of  the  colouring  matter 
of  the  wine  is  complete ;  if  not,  moi'e  hydrate  of  baryta  must  be 
added,  and  the  liquid  re-filtered.  It  is  then  introduced  into  a  flask 
containing  about  250  c.c,  with  50-60  c.c.  of  pure  ether,  strongly 
shaken,  and  allowed  to  settle.  When  the  ether  is  completely  sepa- 
rated from  the  aqueous  liquids,  it  is  drawn  ofi"  by  means  of  a  pipette, 
and  poured  into  a  porcelain  capsule.  A  drop  of  acetic  acid  at  8°  is 
added,  3  or  4  drops  of  di.stilled  water,  and  a  little  white  unwoven 
silk,  consisting  of  ten  threads  a  centimetre  in  length.     If  the  quan- 


PHARMACEUTICAL    CHEMISTRY. 


14^ 


tity  of  magenta  contained  in  the  wine  is  at  all  notable,  acetic  acid 
produces  at  once  a  rose  coloration  ;  but  when  only  minute  traces 
are  present,  the  ether  is  allowed  entirely  to  evaporate.  The  residue 
consists  of  a  small  quantity  of  aqueous  liquid,  in  which  the  silk 
soaks.  The  capsule  is  then  very  gently  heated,  so  as  to  evaporate 
the  balk  of  this  liquid  and  concentrate  the  traces  of  colouring 
matter  in  a  few  drops,  thus  favouring  its  fixation  upon  the  silk. 
This  process,  if  carefully  executed,  reveals  one  hundred-millionth 
part  of  fuchsine  in  wine. 

The  following  directions  are  given  by  Gr.  M.  Fordos  (Ibid.,  980)  : 

10  c.c.  of  the  wine  are  shaken  with  1  c.c.  of  pure  ammonia,  5  to 
10  c.c.  of  chloroform  are  then  added,  the  whole  well  shaken,  and  the 
chloroform,  after  separation  by  a  tap-funnel,  heated  in  a  porcelain 
dish  with  a  piece  of  white  silk  immersed  in  it  ;  when  the  chloro- 
form is  nearly  evaporated,  a  little  water  is  added,  and  the  heating 
continued.  All  the  fuchsine  is  thus  fixed  in  the  silk,  which  becomes 
more  or  less  rose  coloured  if  fuchsine  is  present. 

This  method  permits  of  the  detection  of  extremely  small  quanti- 
ties of  fuchsine,  especially  if  the  wine  be  concentrated,  and  a  very 
small  piece  of  silk  be  used.  Quantitative  results  might  be  obtained 
by  means  of  a  series  of  pieces  of  silk  coloured  more  or  less  deeply, 
with  which  the  piece  coloured  by  the  wine  under  examination  might 
be  compared. 

On  page  1045  of  the  same  journal  a  modification  of  this  process 
is  desci'ibed  by  J.  Fordos  : — 

To  10  c.c.  of  the  wine  to  be  tested  for  fuchsine  1  c.c.  of  am- 
monia and  10  c.c.  of  chloroform  are  added.  The  test-tube  is  to 
be  several  times  inverted,  but  not  shaken,  and  the  chloroform 
drawn  off  by  means  of  a  tap-funnel ;  a  little  water  is  added  to  it, 
and  then  it  is  saturated  with  acetic  acid.  The  fuchsine  now  sepa- 
rates from  the  chloroform,  and  its  aqueous  solution  floats  on  that 
liquid.  Another  modification  is  to  use  only  5  c.c.  of  chloroform, 
and  when  this  has  settled  to  the  bottom  of  the  tube,  to  drop  in  a 
crystal  of  citric  acid.  The  ammonia  being  saturated,  the  fuchsine 
appears  on  the  crystal. 

New  Researches  on  Gallium.  Lecoq  de  Boisbaudran.  (Journ. 
Chein.  Soc,  from  Gomptes  Bendus,  Ixxxii.,  1076.)  Pure  gallium  melts 
at  29"5°  and  liquefies  on  being  held  between  the  fingers.  It  remains 
in  a  state  of  superfusion  with  great  facility,  which  explains  how  a 
globule  of  it  may  remain  liquid  for  several  weeks,  even  though  the 
temperature  may  occasionally  fall  nearly  to  zero.  When  solidified 
the  metal  is   somewhat  hard,   even  at  a  temperature  only  a  few 


150  YEAR-COOK    OP    PHARMACY. 

degrees  short  of  its  fusing  point ;  it  possesses,  however,  some  m.ille- 
abihty,  and  may  be  cut  with  a  knife.  When  melted  it  adheres  to 
glass,  forming  a  mirror  which  is  whiter  than  that  produced  by 
mercury.  Heated  to  redness  in  air  gallium  oxidises  only  superficially, 
and  does  not  volatilise.  Hot  nitric  acid  dissolves  it,  but  the  cold 
acid  scarcely  attacks  it.  The  density  of  the  metal  is  4"7  at  15°, 
determined  as  nearly  as  possible  on  0"0G4  gram  weight  of  it. 

The  metal  was  obtained  by  electrolysing  an  ammouiacal  solution 
of  gallium  su^lphate ;  its  hydrochloric  acid  solution  gave  the  spec- 
troscopic lines  of  gallium,  and  much  more  feebly  those  of  zinc. 

The  oxide  of  gallium  is  very  soluble  in  potash,  but  only  slightly 
so  in  ammonia;  but  the  metal  deposited  from  the  latter  is  solid,  and 
from  the  former  it  is  liquid. 

The  metal  is  deposited  upon  the  platinum  negative  electrode  in 
minute  globules,  from  which  dilute  hydrochloric  acid  dissolves  it 
with  rapid  liberation  of  hydrogen.  The  hydrochloric  solution  was 
not  coloured  by  potassium  iodide,  ammonia,  or  ammonium  sulphide. 

Chemical  Reactions  of  Gallium.  Lecoq  de  Boisbaudran. 
(Ckem.  News,  October,  1876.)  Solutions  o? pure  gallium,  mixed  with 
acid  acetate  of  ammonia,  are  not  rendered  turbid  by  sulphuretted 
hydrogen;  but  if  zinc  is  present  the  sulphide  of  this  metal  is  charged 
with  gallium,  but  the  liquid  is  not  entirely  freed  from  it.  If  the 
salts  of  zinc  are  not  plentiful  enough  to  draw  down  at  once  all  the 
gallium  precipitable  by  sulphuretted  hydrogen,  it  must  be  added  in 
small  portions  until  these  products  no  longer  give  the  ray  Ga  a 
•417"0  in  the  spectroscope.  Only  slight  traces  of  gallium  remain 
then  in  the  liquid.  Oa  proceeding  thus,  the  amount  in  the  pre- 
cipitates appears  to  remain  at  first  almost  constant,  or  at  least  to 
decrease  slowly,  and  then  more  and  more  rapidly,  thus  leaving  but 
a  small  trace  of  gallium  in  the  liquid  These  observations  point 
to  a  combination  between  the  two  substances,  or  perhaps  more 
probably  to  a  surface-attraction  analogous  to  the  fixation  of  a 
Goloui'ing  matter  upon  a  mordant.  It  is  known  that  salts  of  zinc 
slightly  acid  are  precipitated  by  sulphuretted  hydrogen,  the  action 
being  limited  by  the  quantity  of  strong  acid  set  at  liberty.  If  the 
experiment  is  made  with  a  chloride  of  zinc  containing  gallium,  a 
notable  quantity  of  this  metal  falls  along  with  the  sulphide  of  zinc. 
An  ammoniacal  solution  of  the  salts  of  gallium  and  zinc  is  pre- 
cipitated by  hydrosulphate  of  ammonia.  An  excess  of  the  reagent 
does  not  remove  the  gallium,  unless,  indeed,  the  sulphide  of  zinc 
is  in  such  small  quantity  as  to  dissolve  also.  The  case  is  different 
when  the  salt  of  gallium  is  pure.      The  ammoniacal    solution    is 


PHARMACEUTICAL    CHEMISTRY.  lol 

not  rendered  tnrbid  by  the  sulphide  of  ammonium.  If  a  neutral  or 
slightly  acid  solution  of  the  chlorides  of  zinc  and  gallium  is  submitted 
to  fractionated  precipitation  with  sulphide  of  ammonium  containing 
free  ammonia,  the  gallium  is  concentrated  in  the  first  products.  If  an 
ammoniacal  solution  of  zinc  and  gallium  is  submitted  to  the  same  treat- 
ment, the  gallium,  on  the  contrary,  accumulates  in  the  last  precipitates. 

A  New  Process  for  the  Extraction  of  Gallium.  Lecoq  de 
Boisbaudran.  (Comptcs  Eendus,  Ixxxiii.,  G3G.)  The  gelatinous 
precipitate  obtained  by  treating  acid  solutions  of  tbe  gallium-bear- 
ing  mineral  with  excess  of  zinc,  is  dis.solved  in  hydrochloric  acid  ; 
sulphuretted  hydrogen  is  passed  through  the  liquid  ;  and  after  the 
gas  has  been  expelled  from  the  filtrate,  the  latter  is  fractionally  pre- 
cipitated by  sodium  carbonate,  until  gallium  ceases  to  be  throwTi 
down,  and  the  precipitate  no  longer  yields  the  characteristic  spectrum 
of  the  metal.  The  precipitates  are  dissolved  in  sulphuric  acid,  and 
the  solution  is  evaporated  until  vapours  of  sulphuric  acid  cease  to 
be  evolved.  The  residue  is  treated  with  cold  water,  and  after 
dilution  the  solution  is  heated  to  boiling,  when  a  sub-salt  of  gallium 
is  precipitated  and  separated  by  filtering  while  the  liquid  is  hot. 
This  basic  salt  is  dissolved  in  a  small  quantity  of  sulphuric  acid,  a 
slight  excess  of  caustic  potash  is  added,  and  the  filtrate  is  treated 
for  some  time  with  a  current  of  carbonic  acid  gas,  by  which  gallium 
oxide  is  precipitated.  This  is  dissolved  in  the  smallest  possible 
quantity  of  sulphui'ic  acid,  a  small  excess  of  slightly  acid  ammonium 
acetate  is  added,  and  sulphuretted  hydrogen  is  passed  through  the 
liquid,  which  is  then  filtered,  diluted,  and  heated  to  boiling.  The 
greater  part  of  the  gallium  is  now  precipitated,  and  is  separated  by 
filtering  the  hot  liquid.  The  precipitate  is  dissolved  in  sulphuric 
acid,  caustic  potash  is  added  in  slight  excess,  and  the  solution  is 
filtered  and  submitted  to  electrolysis.  The  metallic  gallium  is  easily 
separated  from  the  platinum  pole  by  pressing  with  the  fingers  under 
warm  water,  and  the  product  is  purified  by  treatment  with  nitric 
acid  free  from  chlorine. 

The  Physical  Properties  of  Gallium.  Lecoq  de  Boisbaudran. 
(Covijites  Renclus,  Ixxxiii.,  611.)  The  author  has  prepared  more 
than  half  a  gram  of  gallium ;  when  liquid  it  has  a  silver-white 
lustre,  but  when  crystallized  it  shows  a  tinge  of  blue  and  loses  its 
bi'illiancy.  Its  crystalline  form  is  octohedral.  Its  melting  point, 
averaged  from  six  determinations,  is  30'15°.  It  is  hardly  acted  on 
by  nitric  acid  diluted  with  its  own  volume  of  water.  Its  specific 
gravity  is  o'OoG;  when  crystallized  under  water,  it  decrepitates 
slightly  when  melted. 


I 


^ 


MATERIA    MEDICA. 


PART   II. 

MATERIA  MEDICA. 

Wood  Oil.  Prof.  F.  A.  Fliickiger.  (Pharin.  Journ.,Srd  series, 
vii.,  2).  In  a  note  communicated  to  the  Archiv  der  Pharmacie,  for 
May,  the  author  states  that  he  has  found  that  the  ethereal  oil  of 
dipterocarpus  balsam,  known  as  gurgan  balsam,  or  wood  oil,  when 
dissolved  in  about  20  parts  carbon  bisulphide,  and  a  drop  of  a 
cooled  mixture  of  equal  parts  of  sulphuric  and  nitric  acids  added, 
takes  a  splendid  violet  colour.  A  single  drop  of  the  ethereal  oil  is 
sufficient  to  produce  the  reaction,  aud  the  colour  lasts  sevei-al  hours. 
It  is  not  prevented  by  the  presence  of  resin  or  by  copaiva  balsam;  so 
that  the  reaction  takes  place  with  the  crude  gurgun  balsam,  or  even 
when  that  is  mixed  with  eight  times  its  volume  of  copaiva  balsam. 
The  reaction  can  therefore  be  used  to  detect  the  presence  of  gurgun 
balsam  in  copaiva  balsam.  Under  the  same  conditions,  fish  liver  oil 
and  oil  of  valerian  are  also  coloured  a  beautiful  violet ;  but  only 
transiently  so.  In  order  to  exclude  fish  oil  from  the  test,  it  is  re- 
commended to  distil  off"  the  ethereal  oil ;  although,  on  account  of  its 
high  boiling  point  (2-50°  to  260°  C),  this  is  not  an  agreeable  task. 
Only  a  few  drops  are  required,  however,  for  the  test. 

Should  a  wood  oil  not  correspond  to  this  reaction,  the  author 
thinks  it  might  probably  be  due  to  the  fact  that  some  dipterocarpus 
trees  yield  a  varying  balsam.  The  balsam  is  obtained  in  large 
quantities  from  the  following  species : — Dipteivcarpus  turhinatus, 
Gaertn.  (syn.  D.  Icevis,  Ham.  ;  D.  indiats,  Bedd.),  D.  incanus,  Roxb.; 
D.  zeylanicus,  Thw. ;  D.  trinei'vis,  Bluxae ;  D.  littoralis,  Bl.;  D.  alatus; 
Roxb. ;  D.  hespidns,  Thw.;  D.  gra.cilis,  Bl. ;  I),  retusus,  Bl.  All  these 
species  occur  in  India,  and  in  the  Archipelago,  and  the  last  even  in 
the  Philippines.  Their  resinous  juice  is  used  very  genei-ally  as 
varnish,  hence  the  name  "  -wood  oil."  It  is  hardly  probable  that 
they  all  yield  a  resin  chemically  and  physically  identical.  The 
author  has  found  that  the  oil  distilled  by  him  from  undoubtedly 
true  dipterocarpus  balsam  is  dextrogyre ;  whilst  Werner,  who  first 
examined  gurgun  balsam  in  1862,  speaks  of  it  as  lievogyre.  In  all 
the  specimens  examined  by  the  author  to  the  present  time,  however, 
he  has  found  the  colour  reaction  constant. 


156  YEAR-BOOK    OF    PHARJIACY. 

Another  possible  ground  for  failure  in  obtaining  the  reaction  is  its 
confusion  with  other  licjuids  used  for  simihxr  purposes.  The  balsam 
obtained  from  Hardwichia  pi)i)iata,  Roxb.,  a  legaminaceous  plant,  is 
used  in  Southern  India  in  the  same  medical  cases  as  copaiva  balsam  j 
but  an  authentic  specimen  in  the  author's  possession  is  not  fluor- 
escent like  dipterocarpus  balsam,  and  dissolved  in  carbon  bisulphide 
gives  only  a  yellow  colour  with  the  acid  mixture.  The  author  does 
not  know,  however,  that  it  is  ever  there  called  "  wood  oil." 

A  fat  oil  used  in  enormous  quantities  in  Eastern  Asia  for  paint 
and  varnish,  and  also  as  a  drastic  medicine,  and  very  generally 
called  "  wood  oil,"  is  obtained  from  the  seeds  of  Aleurites  cordata, 
Muller  (syn.  Dryandra  cordata,  Thunb. ;  Elaeococca  Vernicia,  Sprgl. ; 
E.  verrucosa,  A.  Juss),  a  euphorbiaceous  tree.  The  tree  is  common 
in  China  and  Japan,  of  very  characteristic  appearance,  and  is  known 
in  China  as  the  "  tung  tree."  The  oils  from  the  seeds  of  Ricinus 
and  Groton  tiglium  ditFer  in  chemical  properties  and  physiological 
action  from  most  known  oils ;  how  far  such  peculiarities  occur  prin- 
cipally in  the  Eicphorhiacece,  is  a  question  that  yet  requires  answering. 
That  the  "  wood  oil  "  from  the  tung  tree  is  a  fat  worthy  of  notice  is 
shown  by  the  experiments  of  Cloez.  This  chemist  obtained  from 
the  seeds  of  Aleurites  cordata,  by  means  of  carbon  bisulphide,  41  per 
cent,  of  a  fixed  oil,  forming  a  solid  crystalline  mass  below  32°  C. 
When,  on  the  contrary,  the  seeds  were  treated  with  ether,  an  oil  was 
obtained  that  did  not  solidify  even  at  18°  C.  But  what  is  most 
surprising,  is  that  when  prepared  either  by  pressure  or  by  one 
of  the  solvents  mentioned,  and  heated  in  the  air  to  200°  C,  it 
changes  suddenly  into  a  solid  transparent  jelly,  which  is  no  longer 
soluble  in  ether  or  carbon  bisulphide.  This  change  takes  place 
also  after  a  few  days,  when  excluded  from  the  air,  under  the  in- 
fluence of  light  alone.  The  oil  dries  more  rapidly  than  linseed  oil. 
The  principal  acid  in  it  was  obtained  in  crystals  that  melted  at  44°, 
but  very  rajDidly  resinified,  and  therefore  did  not  consist  of  linoleic 
acid. 

The  Therapeutic  Properties  of  Arnica.  Dr.  Patze.  (Neiv 
Remedies,  July,  1876.)  Strong  opinions  having  been  expressed  by 
various  writers  that  the  external  application  of  arnica  is  not  only 
valueless  but  sometimes  positively  noxious,  and  that  arnica  lotion 
applied  to  excoriations  may  occasion  severe  outbreaks  of  acute  in- 
flammation, the  author  offers  the  following  remarks  on  the  subject : — 

Experiments  with  arnica  on  horses  have,  according  to  Schuchardt, 
rendered  the  following  results :  small  doses  accelerated  the  pulse, 
raised  the  temperature  of  the  skin,  increased  the  secretion  of  urine, 


MATERIA    MEDICA,  157 

and  caused  tremor  of  the  muscles.  The  violence  of  these  phenomena 
increased  with  the  augmentation  of  the  dose,  causing  frequent  eva- 
cuations of  fjeces  and  urine,  violent  tremor,  accelerated  respiration, 
and  prostration.  Injections  of  an  infusion  of  arnica-flowers  into 
the  veins  caused  considerable  excitation,  soon  followed  by  intense 
languidness,  vertigo,  and  even  death  ;  and  on  examination,  the  organs 
of  the  chest  and  abdomen,  the  cerebrum  and  spine,  were  found  en- 
gorged with  blood. 

In  man  the  series  of  symptoms  are  the  following  :  any  part  of  the 
arnica-plant  applied  to  the  skin  causes  an  itching,  burning  sensa- 
tion, accompanied  by  redness ;  though  its  fragrance  is  agreeable,  it 
will,  in  closer  proximity,  cause  sneezing,  so  much  so,  that  the 
Savoyards  are  using  it  instead  of  snuff.  Small  doses  of  4  to  10 
grains  exert  an  irritating  effect  on  the  fauces  and  larynx,  on  the 
stomach  and  the  alimentary  canal,  manifesting  itself  by  a  burning, 
scratching  sensation,  cardialgia,  abdominal  pains,  nausea,  belching, 
vomiting,  frequent  evacuations,  the  circulation  is  accelerated,  accom- 
panied by  increase  of  warmth  of  the  body ;  the  secretions  are  in- 
creased, especially  those  of  the  urine,  the  skin,  and  the  lungs.  The 
continued  use  of  the  arnica  will  cause  numbness  of  the  head,  vertigo, 
mental  depression,  restless  sleep,  oppression  of  the  lungs,  jerking 
pains  like  electric  strokes,  in  the  extremities,  etc. ;  increase  of  the 
dose  will  aggravate  all  these  phenomena,  especially  the  affections  of 
the  brain. 

The  hot  infusion  acts  more  severely  than  the  tincture,  and  the 
flowers  are  more  exciting  than  the  root.  This  series  of  symptoms 
indicates  that  arnica  may  find  its  place  in  all  those  diseases  which 
manifest  a  character  of  torpor,  wherever  an  acceleration  of  the 
circulation  is  desirable,  in  order  to  remove  and  scatter  stagnating 
humours. 

Arnica  is  in  Germany  so  extensively  and  frequently  used,  that 
some  apothecaries  have  to  keep  the  infusion,  by  the  quart,  on  hand, 
preparing  it  every  morning  fresh  (5  j.  of  the  flowers  steeped  for  15 
minutes  in  6  ounces  of  boiling  water).  It  has  maintained  its  old 
reputation  in  a  variety  of  cases,  especially  where  the  vitality  of  the 
nerve-centres,  brain  and  spine,  is  oppressed ;  in  extravasations, 
paralysis  consequent  upon  apoplectic  strokes,  rheumatism,  catarrh, 
pleurisy  and  pneumonia,  in  traumatic  commotions  of  the  brain,  in 
typhoid  fevers  with  torpor  and  paralytic  affections,  etc. 

The  external  use  of  arnica  is  very  limited,  and  especially  contra- 
indicated  in  recent  traumatic  cases;  it  should  never  be  applied 
before  all  tendency  to  inflammation  is  removed  by  the  antiphlogistic 


158  YEAR-BOOK    OF    PHARMACY. 

applications  ;  it  can  therefore  seldom  find  its  place  before  the  lapse 
of  seven  days  after  the  injury;  then,  and  not  before  then,  the  tinc- 
ture, properly  diluted  in  combination  with  other  remedies  for  the 
stimulation  of  the  capillary  vessels,  may  be  applied,  perhaps  like 
this  : — l]i.  TinctnriB  flor.  Aruicce,  3  ss ;  Aceti,  5  ss  ;  Aq.  Camphoraj, 
5  vj.     d.  g.  for  external  nse. 

Olive-tree  Bark.  L.  Thibon.  (Bepert.  cle  Pharm.,  187G,  558.) 
This  bark,  which  is  favourably  spoken  of  as  a  febrifuge,  contains  a 
principle  which  the  author  has  named  oliverine.  It  is  prepared  by 
evaporating  an  aqueous  decoction  of  the  bark  to  the  consistence  of 
a  syrup,  precipitating  by  strong  alcohol,  filtering,  and  precipitating 
the  filtrate  by  oxalic  acid.  The  filtrate  from  the  last  precipitate 
deposits  the  oliverine  during  evaporation.  When  purified  it  forms 
yellow  granules  having  a  very  bitter  taste.  Dr.  Fabry  has  admin- 
istei-ed  the  substance  in  doses  of  0"1  to  0"3  gram  four  or  five  times 
a  day,  and  speaks  highly  of  its  effects.  It  is  recommended  in  cases 
where  quinine  is  indicated. 

Goto  Bark  and  its  Crystallizahle  Constituents.  J.  Jobst.  (From 
Ber.  cler  deiitsch.  Chem.-Ges.,  ix.,  633;  Pharm.  Journ.,  3rd  series,  vii.. 
495).  The  author  reports  that  the  crystallizable  body  some  mouths 
since  separated  by  him  from  Bolivian  coto  bark,  and  named  by  him 
"  cotoin,"  bas  since,  on  account  of  its  excellent  anti-diarrhceic  action, 
been  used  to  a  considerable  extent ;  but  unfortunately  the  importation 
of  the  crude  material  has  not  kept  pace  with  the  demand.  After  a 
lono-  interval  a  larger  parcel  of  coto  bark  came  into  his  possession  ; 
but  the  new  bark  showed  marked  ditferences  in  its  exterior,  which 
were  also  manifest  in  the  taste  and  smell.  Upon  the  extraction  of 
the  bark  by  the  process  given  for  cotoin,  a  body  similar  to  cotoin, 
crystallizing  in  yellow  flakes,  was  obtained,  which,  however,  ^as 
not  cotoin,  and  difi'ered  from  it  essentially  in  its  reactions. 

In  the  first  place,  the  new  body  wants  the  biting  taste  of  cotoin ; 
further,  it  is  much  more  difficultly  soluble  in  water,  alcohol,  ether, 
ammonia,  and  potash  solution.  Concentrated  sulphuric  acid  does 
not  give  with  it  the  characteristic  reaction  of  cotoin,  but  only  a 
yellow  solution  ;  lead  acetate  causes  no  precipitate. 

The  author  proposes  for  this  substance  the  name  of  "  paracotoin," 
and  states  that  in  the  last  imported  coto  bark  several  other  crystal- 
lizable bodies  are  contained  in  smaller  quantities. 

Upon  making  complaint  respecting  the  varying  quality  of  the 
bark,  the  author  was  told  that  the  parcel  in  question  came  from  the 
banks  of  the  river  Mapiri,  in  Bolivia,  and  represented  the  best  coto 
that  it  furnished.     No  further  information  could  be  obtained. 


MATERIA    3IEDICA.  159 

The  author's  stock  of  cotoin,  pi'epared  from  the  original  coto 
bark,  being  almost  exhausted,  he  was  induced  by  the  undoubted 
similarity  of  the  two  barks  and  their  principal  products,  to  seek  to 
ascertain  the  therapeutic  action  of  the  new  body.  The  experiment 
was  made  by  Herr  Burkart.  He  found  that  paracotoin  exercises 
the  same  anti-diarrhceic  action  as  cotoin,  the  difference  between  the 
two  preparations  being  only  of  one  degree;  paracotoin,  in  accordance 
with  its  inferior  solubility,  showing  a  somewhat  weaker  action  than 
cotoin,  consequently  the  dose  slightly  varies.  In  his  therapeutic 
experiments,  Herr  Burkart  administered  it  either  in  the  powder 
form,  O'l  gram  with  0'2  grams  of  saccharum  album  every  three 
hours,  or  in  emulsion,  0'5  gram.  On  account  of  its  insolubility,  the 
powder  form,  in  the  above  doses,  was  preferred ;  the  patients  takino- 
the  powder  more  readily  on  account  of  its  complete  tastelessness. 

A  relation  appears,  therefore,  to  exist  between  the  two  coto  barks 
similar  to  that  observed  in  the  case  of  the  cinchonas ;  where  barks 
have  been  found  within  narrow  limits  in  which  alternately  quinine 
or  cinchonidine  or  cinchouine  predominate. 

The  author  is  engaged  in  an  investigation  of  the  relation  in  which 
cotoin,  paracotoin,  and  the  other  crystalline  constituents  of  the  coto 
bark,  stand  to  each  other  in  respect  to  their  chemical  composition. 

The  Constituents  of  Coto  Bark.  J.  Jobs t  and  0.  Hesse.  {Ber. 
cler  deidsch.  Chem.-Ges.,  x.,  249,  from  Pharm.  Journ.,  3rd  series,  vii., 
1019.)  This  bai'k  has  been  further  examined  by  the  authors,  and 
the  results  have  been  communicated  to  the  Berlin  Chemical  Society. 
The  powdered  bark  extracted  with  ether  yielded  a  yellow-brown  solu- 
tion, which  left,  after  evaporation  of  the  ether,  a  brown  resinous  residue 
that  showed  after  a  time  an  abundant  crystallization.  The  crystal- 
line mass  consisted  principally  of  three  bodies,  to  which  the  authors 
have  given  the  names  "paracotoin,"  "oxyleucotoin,"  and  "leucotoin;" 
these  were  separated  by  fractional  crystallization  from  hot  alcohol. 

Paracotoin  (C^g  A^,  Og)  forms  yellow  scales,  easily  soluble  in 
chloroform,  ether,  and  boiling  alcohol ;  less  soluble  in  cold  alcohol, 
benzin,  petroleum  spirit,  and  boiling  water.  From  the  solution  in 
boiling  water  it  is  obtained  on  cooling  in  almost  colourless  scales. 
In  alcoholic  solution  it  has  no  reaction  on  litmus  paper,  and  is  taste- 
less. In  ammonia  it  is  insoluble ;  and  from  hot  ammoniacal  alco- 
holic solution  it  crystalhzes  unaltered.  In  dilute  potash  or  soda  it 
dissolves  with  a  yellow  colour,  but  only  in  small  proportion.  In 
strong  sulphuric  acid  it  forms  a  yellow  solution,  but  this  upon 
heating  becomes  lighter.  Perchloride  of  iron  presents  no  reaction 
with  it.     Paracotoin  melts  at  152"    (uncorrected)  to  a  yellow  liquid, 


160  YEAR-BOOK   OF    PHARMACY. 

which  upon  cooling  takes  a  radiating  crystallization.  At  a  higher 
temperature  it  sublimes  in  yellow  shining  scales. 

By  the  action  of  baryta  water  paracotoin  is  converted  into  para- 
cotoic  acid,  according  to  the  equation, — 

This  acid  forms  a  chrome  yellow  amorphous  powder,  readily  soluble 
in  ether  and  alcohol,  but  almost  insoluble  in  hot  benzin.  The 
alcoholic  solution  has  a  decided  acid  reaction,  and  upon  evaporation 
leaves  the  acid  amorphous.  The  same  acid  is  formed  when  para- 
cotoin is  boiled  with  dilute  potash  solution,  or  only  heated  to  80°  C; 
but  then  there  is  also  formed  a  smaller  quantity  of  another  pi'oduct, 
which  has  been  named  "  paracumarhydrin."  When  the  solution  is 
boiled  it  escapes  with  the  steam.  Paracumarhydrin,  Cg  Hg  O3,  forms 
delicate  white  scales,  melting  at  85°  C.  (uncorrected),  readily  soluble 
in  alcohol  and  ether,  less  so  in  hot  water,  from  which  upon  cooling 
it  is  again  deposited  in  scales.  Its  formation  from  paracotoin  may 
probably  be  represented  as  follows  : — 

CigHioOg  +2HoO  =  C02  +  2C9H8  03. 
Paracumarhydrin  has  a  smell  recalling  that  of  cumarin  ;  and  when 
it  is  rapidly  heated  the  odours  of  oil  of  winter-green  and  oil  of  bitter 
almonds  are  noticeable.  Upon  attempting  to  redistil  it  with  water 
vapour  only  a  small  portion  passes  over,  the  greater  part  remaining 
dissolved  in  the  water  in  the  retort.  Upon  shaking  this  aqueous 
solution  with  ether,  and  evaporating  the  latter,  white  crystalline 
scales  are  obtained,  having  an  extremely  pleasant  taste,  and  melting 
at  81°  to  82°  C.  The  same  substance  results  upon  treating  para- 
cumarhydrin with  zinc  chloride.  Apparently  in  both  cases  it  loses 
water  and  forms  the  paracumarin  corresponding  to  paraoxybenzoic 
acid. 

Comparison  of  this  substance  with  cumarin  shows  that  it  resembles 
it  only  in  smell.  Whilst  cumarin  is  deposited  from  dilute  alcohol 
in  four-sided  prisms,  the  supposed  paracumarin  forms  shining  scales. 
The  fusing  points  also  diifer.  Zwenger  and  Bodenbeuder  found 
that  for  cumarin  prepared  from  Melilotus  qficinnlis,  it  was  67° ;  and 
Perkins,  for  that  from  aceto-salicyl  aldehyd  between  67°  and  67'5° 
C.  By  treatment  of  paracotoin  with  caustic  potash,  an  acid  was 
obtained  crystallizing  in  small  needles,  and  melting  at  200°,  or  nearly 
the  temperature  given  by  Tiemann  and  Mendelsohn  for  paracumaric 
acid.  The  crystals,  however,  were  yellow,  and  gave  on  combustion 
oifly  60"9]  per  cent,  of  carbon,  and  4U5  of  hydrogen  ;  paracumaric 
acid  requiring  65'88  per  cent,  of  carbon,  and  4*87  per  cent,  of 


MATERIA   MEDICA.  161 

hydrogen.  When  fused  with  potassium  hydrate,  paracotoin  gave 
off  a  faint  smell  of  paracumarhydrin ;  but  an  acid  was  formed,  with 
evolution  of  hydrogen,  corresponding  with  protocatechuic  acid  in 
its  behaviour  towards  ferric  chloride,  though  differing  in  other 
respects.  A  volatile  acid  (apparently  formic  acid)  was  also  formed, 
and  a  brown  resinic  acid. 

Oxyleucotoin  (Cji  Hng  0-)  can  be  separated  from  leucotoin  by  crys- 
tallization from  alcohol,  in  which  the  latter  is  very  soluble.  It 
forms  thick,  heavy,  white,  rectangular,  obliquely  truncated  prisms, 
melting  at  133°,  and  solidifying  amorphous  on  cooling.  It  dissolves 
freely  in  hot  alcohol,  ether,  and  chloroform ;  less  so  in  cold  alcohol, 
and  is  nearly  insoluble  in  cold  water  and  alkalies.  It  is  tasteless, 
and  neutral,  and  in  chloroform  solution  does  not  affect  polarized 
light.  Strong  sulphuric  acid  colours  it  dark  yellow.  Strong  nitric 
acid  dissolves  it  upon  warming  with  a  blue-green  colour,  leaving  a 
bluish  black  resin  that  forms  a  blue-green  solution  in  alcohol.  When 
fused  with  potassium  hydrate,  oxyleucotoin  yields  a  crystallizable 
acid,  giving  a  green  colour  with  salts  of  iron,  and  also  differing 
from  pyrocatechuic  acid. 

Leucotoin  (Co^  Hoq  Oq)  resembles  oxyleucotoin  in  its  behaviour  to 
sulphuric  and  nitric  acids ;  dissolves  very  freely  in  alcohol,  benzin, 
and  ether;  forms  very  slender  white  prisms  melting  at  97°.  In 
chloroform  solution  it  has  no  action  on  polarized  light.  It  occurred 
in  considerable  quantity  in  the  bark  examined. 

Hydrocotoin  (Coo  Hoq  Oq)  remained  dissolved  in  the  mother-liquor 
from  which  the  foregoing  substances  were  obtained.  This  liquor, 
being  evaporated,  left  a  brown  resin,  which  was  exhausted  with  very 
dilute  caustic  alkali,  excess  of  hydrochloric  acid  added  to  the  solu- 
tion, and  the  resulting  reddish  yellow  flocculent  precipitate  dissolved 
in  a  little  hot  alcohol,  from  which  the  hydrocotoin  crystallized  on 
cooling  in  shining  pale  yellow  prisms.  From  boiling  water  slender 
white  needles  were  obtained.  Hydrocotoin  is  neutral,  tasteless,  and 
in  chloi'oform  solution  without  effect  on  polarized  light.  It  dis- 
solves in  alkalies  with  a  yellow  colour  ;  and  is  again  precipitated  by 
acids,  even  carbonic.  Strong  sulphuric  acid  forms  with  it  a  yellow, 
and  hot  nitric  acid  a  purple  red  solution  ;  from  which,  upon  dilution 
with  water,  a  purple  red  precipitate  soluble  in  cold  alcohol  separates. 
When  heated  with  manganese  and  sulphuric  acid,  or  upon  combus- 
tion of  one  of  its  lead  salts,  hydrocotoin,  gives  off  an  odour  resembling 
hyacinthin. 

Cotoin,  the  substance  obtained  from  the  coto  bark  first  examined, 
the  authors  now  represent  by  the  formula.  Coo  Hjg  Oq  ;  so  that  para- 

M 


162  YEAR-BOOK    OP    PHARMACY. 

cotoin  would  appear  to  be  a  liomologue  differing  by  C3  H^,.  Hydro- 
cotoin  appears  to  differ  from  cotoin  in  containing  two  atoms  more 
of  hydrogen  in  the  molecule. 

The  authors  state  that  Dr.  Burkart,  of  Stuttgart,  is  making  ex- 
periments with  paracotoin,  oxyleucotoin,  and  leucotoin  ;  the  results 
of  which  will  be  reported  in  a  medical  periodical.  Meanwhile,  para- 
cotoin, notwithstanding  its  high  price,  which  is  probably  temporary, 
is  finding  a  daily  use  as  a  remedy  against  all  kinds  of  diarrhoea. 

Adonis  Vernalis.  F.  Linderos.  (Liebig's  Annalen,  182,  3G5.) 
The  dried  leaves  of  this  plant  are  employed  on  the  Continent  as  a 
drastic  purgative.  According  to  the  author's  investigation,  the 
leaves  gathered  at  the  time  of  flowering  contain,  when  dry,  10  per 
cent,  of  aconitic  acid,  which  appears  to  be  combined  with  calcium 
and  potassium. 

The  Chemical  Constituents  of  Angelica  Root.  C.  Brunner. 
(Neues  Eepert.,  xxiv.,  641  ;  Journ.  Chem.  Soc,  1876,  939.)  The  fol- 
lowing analysis  of  angelica  root  was  given,  many  years  ago,  by  Johw  : 
— 300  parts  contain :  colourless  volatile  oil  of  a  penetrating  odour, 
2  parts;  resin,  with  sour  taste,  20;  other  extractives,  37"5  ;  gum, 
100"5  ;  inulin,  12 ;  product  soluble  in  caustic  alkali,  probably  com- 
bined with  albumen,  22  ;  woody  tissue,  with  a  trace  of  matter  soluble 
in  potash,  90 ;  water,  16  parts.  Similar  figures  were  also  obtained 
by  Buchholz  and  Brandes,  who  found  six  per  cent,  of  "  angelica 
balsam."  This  product  was  afterwards  found  by  A.  Buchner  to 
contain  an  agreeably  smelling,  camphoraceous,  essential  oil,  a  vola- 
tile acid,  a  waxy  substance,  an  amorphous  resin,  and  a  crystalliz- 
able  principle  analogous  to  imperatorin  and  peucedanin,  to  which 
he  applied  the  term  angelicin.  The  author  prepared  this  substance 
from  fifty  pounds  of  root  grown  near  Schweinf art.  After  complete 
extraction  with  boiling  alcohol,  and  evaporation  of  the  extract,  1090 
grams  of  "  balsam  "  separated,  insoluble  in  water ;  whilst  an  aqueous 
liquid  was  also  obtained,  in  which  the  balsam  floated.  This  liquid 
was  found  to  contain  cane  sugar,  the  values  73'2  and  7304<  being 
obtained  by  the  polariscope  ;  whilst  the  specific  rotatory  power  given 
in  text-books  is  7'd'S4:. 

The  "  balsam  "  thus  obtained  was  heated  with  aqueous  caustic 
potash  (500  grams  balsam,  180  of  solid  caustic  potash)  until  a 
homogeneous,  brownish  red,  thick  fluid  was  obtained ;  on  distillation 
this  furnished  a  small  quantity  of  an  ethereal  oil.  When  this  ceased 
coming  over,  the  residue  was  evaporated  to  a  thick  syrup,  and  dis- 
solved in  water.  After  standing  all  night,  and  filtering,  a  minute 
quantity  of  insoluble  matter  was  obtained,  possibly  angelica  wax. 


MATERIA    MEDICA.  163 

The  liquid  did  not  deposit  crystals  of  angelicin  on  standing ;  it  was 
therefore  again  evaporated,  and  the  residue  treated  with  alcohol, 
whereby  much  resin  was  left  undissolved  ;  the  filtrate  was  saturated 
with  carbonic  acid,  to  remove  potash;  and  the  filtrate  from  the  crystals 
of  potassium  carbonate  evaporated  to  a  small  balk,  and  then  treated 
with  ether  as  long  as  the  latter  became  coloured.  By  spontaneous 
evaporation  the  ethereal  extract  gave  a  smeary  residue,  containing  a 
few  crystals ;  this  residue  became  much  more  crystalline  on  stirring 
it  up  with  alcohol,  and  again  leaving  it  to  evaporate  spontaneously. 
Finally,  the  mother-liquors  were  removed  by  the  filter  pump,  and 
washing  with  80  per  cent,  spirit.  The  crystals  of  angelicin  thus 
obtained  weighed,  after  purification  by  recrystallization,  only  about 
0"8  gram.  This  small  yield  appeared  to  be  due  to  the  fact  that  the 
roots  employed  had  been  dried  in  an  oven ;  from  thirty  pounds  of 
air-dried  roots  a  much  larger  yield  was  obtained  by  the  same  pro- 
cess. Finally,  about  4  grams  of  pure  angelicin  were  isolated,  con- 
stituting fine  white  silky  plates,  destitute  of  taste  and  odour  ;  slightly 
soluble  in  cold,  more  so  in  hot,  alcohol ;  and  readily  soluble  in  ether, 
choloroform,  carbon  disulphide,  benzin,  oil  of  turpentine,  and  warm 
olive  oil.  On  analysis  this  substance  gave  numbers  agreeing  with 
the  formula  Cj^gHgQ  0.  From  these  figures,  and  the  general  properties 
of  the  substance,  it  appears  to  be  identical  with  the  hijdrocarotin  of 
Husemann.  It  melts  at  126'5°  to  yellowish  oily  drops,  which  solidify 
at  118°  to  an  amorphous  mass,  soluble  in  alcohol  and  ether,  but  not 
crystallizing  from  these  solutions  (the  original  substance  crystallizes 
readily  in  forms  belonging  to  the  monoclinic  system).  Concentrated 
hydrochloric  acid  does  not  change  angelicin  ;  but  fuming  nitric  acid 
dissolves  it  with  evolution  of  gas.  Concentrated  sulphuric  acid  dis- 
solves it  to  a  red  fluid,  depositing  brownish  white  flakes  on  dilation 
with  water.  Fusion  with  caustic  potash,  and  treatment  with  bromine, 
give  rise  to  the  formation  of  amorphous  coloured  products. 

The  resin  insoluble  in  alcohol,  obtained  as  above  described,  was 
fused  with  caustic  potash  in  a  silver  dish  ;  the  product,  dissolved  in 
water  and  acidulated  with  sulphuric  acid,  evolved  acetic,  butyric, 
and  other  fatty  acids ;  and  the  aqueous  liquid  yielded  to  ether  a 
mixture  of  two  substances,  separable  by  addition  of  lead  acetate. 
The  precipitate  thus  thrown  down  gave,  after  decomposition  by 
sulphuretted  hydrogen,  a  small  quantity  of  a  crystalline  acid,  colour- 
ing ferric  chloride  green,  the  coloi-ation  becoming  deep  red  on 
further  addition  of  sodium  carbonate.  With  silver  nitrate  this  gave 
no  precipitate  ;  but  on  further  addition  of  ammonia  immediate  reduc- 
tion ensued.     Hence  this  product  was  doubtless  protocatechuic  acid. 


164  YEAR-BOOK   OF   PHARMACY. 

The  filtrate  from  the  lead  precipitate  was  treated  with  sulphuretted 
hydrogen,  and  evaporated,  whereby  crystals  were  obtained  consisting 
apparently  oiresorcin;  they  sublimed  between  watch-glasses,  coloured 
ferric  chloride  violet,  reduced  silver  nitrate  on  warming,  gave  a  highly 
fluorescent  product  on  treating  with  phthalic  acid  and  sulphuric 
acid  (Baeyer's  test),  and  formed  a  body  which — like  diazoresorcin — 
was  red,  and  became  blue  on  adding  ammonia,  on  treating  the 
ethereal  solution  with  nitric  acid  containing  niti'ous  acid  (Weselsky's 
test). 

The  liquid  from  which  angelicin  was  dissolved  out  by  ether,  as 
above  described,  contained  the  potash  salt  of  a  volatile  acid,  which 
appeared  to  be  angelic  acid.  This  was  obtained  by  adding  sulphuric 
acid  and  distilling ;  oily  drops  insoluble  in  water  thus  came  over, 
and  on  collecting  these  and  placing  them  in  a  freezing  mixture, 
crystals  separated,  which  were  drained  and  pressed  in  filter  paper, 
and  these  possessed  all  the  properties  of  angelic  acid.  Valerianic 
and  acetic  acids  came  over,  together  with  the  angelic  acid,  on  the 
first  distillation. 

Some  Constituents  of  Cubebs.  E.  Schmidt.  (Ber.  der  deutsch. 
Ghem.-Ges.,  1877, 188.)  The  author's  statement  that  the  stearopten 
of  oil  of  cubebs  is  a  hydrate  of  the  oil  corresponding  to  the  formula 
Ci5  Hog  0  =  Ci5  Ho^  +  Ho  0,  has  been  called  in  question  by  J.  Jobst 
and  O.  Hesse,  who  regard  this  body  as  an  oxidation  product  of  the 
oil,  the  composition  of  which  is  represented  by  the  formula  C-^-  H04,  0. 

The  author  has  therefore  resumed  his  investigation  of  this  sub- 
ject, and  has  obtained  results  completely  confirming  his  previous 
statements. 

Cubeb-camphor  fuses  at  65°  C,  and  gives  off  water  when  heated 
in  a  sealed  tube  to  200°  C.  When  kept  over  sulphuric  acid  under  a 
bell  jar,  it  also  parts  with  water,  and  is  converted  into  a  transparent 
oily  liquid  having  the  same  boiling  point  as  oil  of  cubebs  (250°-260°). 
Repeated  analyses  of  the  camphor  yielded  numbers  establishing  the 
correctness  of  the  formula  C^j  Hoj,  +  Hg  0. 

Cubebin,  which  the  author  formerly  described  as  a  cry  stall  izable 
resin  of  the  formula  C33  Hg^  0^,  has  also  been  re-examined,  and  is 
now  regarded  by  him  as  an  oxidation  product  of  the  oil,  answering 
to  the  formula  Cgg  Hgg  Og,  which  agrees  with  the  formula  found  by 
Heldt. 

An  Adulteration  of  Aconite  Root.  E.  M.  Holmes.  (Pharm. 
Jour7i.,  3rd  series,  vii.,  749.)  Aconite  root  possesses  such  powerful 
properties,  that  it  is  very  important  the  medicinal  article  should  be, 
as  far  as  possible,  of  uniform  strength  and  quality.     Yet  this  is  by 


MATERIA    MEDIUA. 


165 


no  means  the  case,  for  it  is  difficult  to  find  in  a  commercial  sample 
one  root  in  a  dozen  which  upon  fracture  appears  sound  and  in 
good  condition.  This  is  due,  according  to  Hanbury,  to  its  being 
gathered  indiscriminately  by  peasants,  who  regard  neither  the  most 
advantageous  time  for  collection,  nor  the  proper  species.  From  the 
cheapness  of  the  root,  and  from  the  fact  that  few  roots  have  the  dis- 
tinctly conical  appearance  of  aconite,  it  is  evident  that  it  would 
scarcely  pay  to  adulterate  it.  Adulteration  then  must  either  result 
from  careless  collection,  or  from  accidental  admixture. 

The  root  which  has  lately  been  found  mixed  with  aconite  is  that 
of  masterwort,  Imperatoria  ostndhium,  L.,  an  umbelliferous  plant, 
official  in  the   Edinburgh  Pharmacopoeia  so  late  as  1792.     It  is  a 


Fig.  1.    IHPEEATOEIA    OSTRUTHIUil.* 

native  of  mountainous  countries,  and  grows  in  similar  districts  to 
those  in  which  aconite  is  found.  As  it  is  still  official  in  the  German 
Pharmacopoeia,  its  accidental  occurrence  in  aconite  root  from  Ger- 
many is  not  surprising. 

Its  value  in  this  country  is  double  that  of  aconite  root,  and  it  is  ob- 
vious therefore  that  it  has  not  been  purposely  used  as  an  adulteration. 

In  the  sample  examined,  the  masterwort  root  amounted  to  about 
6  per  cent. 

The  ■woodcuts  of  this  and  subsequent  illustrations  were  kindly  lent  by  the 
Editor  of  the  Pharmaceutical  Journal. 


166 


YEAR-BOOK    OF    PHARMACY. 


The  characters  by  which  it  may  be  distinguished  from  aconite  root 
are  as  follows  : — 

The  root-stock  (Fig.  1),  for  it  is  properly  so  called,  is  less  tapering 
than  aconite  root,  is  slightly  compressed,  and  exhibits  several  warty 
zones,  indicating  periods  of  growth.  The  whole  of  the  root-stock  is 
finely  wrinkled  transversely,  so  as  to  give  it  a  somewhat  annulated 
appearance.  The  transverse  section  presents  very  marked  charac- 
ters. The  central  portion  is  of  a  yellowish  white  colour,  and  exhibits 
a  more  or  less  complete  ring  of  brownish  dots.  The  portion  next 
the  bark  presents  elongated  dots  of  a  paler  colour,  which  give  this 


Fig.  2.       ACONITUM    XAPELLU8,    L. 


portion  of  the  section  a  radiate  appearance.  With  the  aid  of  a  lens, 
these  dots  are  seen  to  be  filled  with  an  oily  or  resinous  substance. 
The  cortical  portion  is  very  thin.  The  root-stock  has  an  odour  com- 
parable to  braised  ivy  leaves,  or  to  the  plant  commonly  known  as 
cow  parsley  (Chcerophyllum  sijlvestre,  L.),  and  a  pungent  slightly 
bitter  taste. 

Aconite  root  is  very  variable  in  appearance  internally  ;  frequently 
the  centre  is  quite  hollow.  Some  pieces  have  a  brownish  colour, 
others  are  white  and  starchy,  and  a  few  present  a  resinous  fracture. 
In  a  sound  root,  however,  which  is  usually  starchy  or  slightly  resin- 


MATERIA    MEDICA. 


167 


ous,  a  faint  line  may  generally  be  traced,  which  marks  out  the  medi- 
tullinm.  This  hne  has  usually  five  to  nine  prominent  angles  (see 
Fig.  2),  the  number  of  angles  being  larger  as  the  section  approaches 
the  top  of  the  root.  If  the  root  be  wetted  and  examined  with  a  lens, 
the  line  is  seen  to  consist  of  an  irregular  line  of  vessels,  which  form 
small  bundles  in  the  apex  of  the  projecting  angles.  The  cortical 
portion  occupies  nearly  half  of  the  circumference  of  the  root. 

From  the  above  characters  it  will  be  observed  that  the  presence  of 
oil  receptacles  in  the  masterwort  root  at  once  distinguishes  it  from 
aconite.  A  spirituous  tincture  of  masterwort  when  dropped  into 
water  gives  a  blue  fluorescence  resembling  that  of  quinine,  and  a 
slight  milkiness,  and  communicates  to  the  water  its  peculiar  odour. 
By  these  characters  its  presence  might  probably  be  detected  in  a 
mixture  containing  tincture  of  aconite.  Although  the  small  per- 
centage in  the  sample  examined  would  lead  to  but  very  slight  dim- 
inution of  strength  in  the  tincture  of  aconite  made  from  it,  yet  the 
appearance  and  odour  communicated  to  a  mixture  containing  such  a 
tincture,  might  lead  to  much  inconvenience  in  pharmacy,  and  throw 
discredit  upon  the  dispensing  department. 

It  is  quite  time  that  the  attention  of  cultivators  of  medicinal 
plants  in  this  country  should  be  drawn  to  the  bad  quality  of  the 
imported  root,  and  that  attempts  should  be  made  to  cultivate  it  ex- 
tensively in  this  country.  It  is  very  probable  that,  as  in  the  case  of 
henbane,  a  good  article  would  command  a  fairly  remunerative  price. 
It  is  obvious,  also,  that  until  it  is  possible  to  obtain  a  plentiful  supply 
of  the  roots  oi  Aconitum  Napellus,  free  from  any  admixture  of  other 
species,  it  will  not  be  possible  to  obtain  an  accurate  knowledge  of 
the  alkaloids  contained  in  that  species. 

Kosin.  Prof.  Buchheim.  {Bepertor  cler  Phcmn.,  xxv.,  423.) 
The  author's  previously  published  observations  on  the  comparative 
merits  of  Merck's  crystallized  kosin  and  Bedall's  koussin  have  led 
Prof.  Fliickiger  to  the  conclusion  that  the  anthelmintic  action  of  the 
first  named  pi-eparation  is  much  inferior  to  that  of  the  latter  (see 
Year-Booh  of  Phannacy,  1875,  pp.  19-22).  Prof.  Buchheim  now 
states  that  he  does  not  agree  with  this  conclusion.  He  considers 
kosin  as  better  suited  for  medicinal  administration  than  koussin,  and 
as  quite  equal  to  it  in  its  anthelmintic  properties.  Bedall's  koussin 
appears  to  be  kosin  which  has  undergone  a  partial  change  through 
the  energetic  action  of  the  lime  employed  in  its  preparation. 

Admixture  of  White  Hellebore  with  Valerian  Koot.  Prof. 
Bentley.  (Pharm.  Journ.,'3vd  series,  vii.,  649.)  Having  recently 
detected  the  rhizome  and  rootlets  of   Veratricm  alhuvi  in  a  parcel 


168  YEAR-BOOK    OF    PHARMACY. 

of  valerian,  the  author  calls  attention  to  the  principal  distinctive 
characters  between  the  two  drugs  as  exhibited  in  the  specimen 
examined  by  him. 

In  the  first  place,  the  veratrum  rhizomes  are  either  crowned  by  a 
conical  bud  of  unexpanded  leaves,  or  by  the  fibrous  reniains  of 
leaves  which  they  once  boro.  These  leaves  at  first  sight  bear  some 
faint  resemblance  to  those  found  at  the  end  of  the  creeping  shoots 
or  stolons  which  are  developed  from  the  root-stock  of  the  true  vale- 
rian plant,  and  by  which  that  plant  is  propagated  ;  but  the  leaves 
in  the  latter  plant  are  opposite  to  each  other,  and  overlap  at  their 
base,  while  those  of  veratrum  form  conceutric  sheaths,  which  are 
arranged  one  within  the  other.  Moreover,  in  commercial  specimens 
of  valerian  root,  such  stolons  are  rarely  or  ever  found.  The  presence 
and  arrangement  of  these  leaves  ought,  therefore,  at  once  to  lead  to 
the  detection  of  white  hellebore  rhizomes  when  mixed  with  those  of 
valerian. 

Secondly,  the  white  hellebore  rhizomes  are  much  larger  than  those 
of  the  valerian,  and  also  entire ;  whereas  the  valerian  are  commonly 
more  or  less  cut.  The  rhizomes  of  veratrum  are  also  of  a  darker 
colour,  and  when  of  any  length,  marked  below  with  the  pits  and 
scars  of  old  roots. 

Thirdly,  a  transverse  section  of  white  hellebore  rhizome  presents 
a  large  central  woody  or  spongy  portion  of  a  whitish  or  pale  buff 
colour,  which  is  separated  by  a  fine  wavy-crenate  ring  from  an  outer 
broad  white  part  which  is  coated  by  a  thin  dark  brown  or  blackish 
bark-like  portion.  The  appearance  of  this  transverse  section,  par- 
ticularly that  of  the  undulating  ring,  is  very  different  from  a  similar 
section  of  valerian  rhizome,  which,  although  whitish  at  first,  presents 
in  commercial  specimens  a  dark  brown,  firm  and  horny  central 
portion,  separated  by  a  dark  interrupted  cambial  zone  from  the 
cortical  part,  which  is  also  of  a  brown  colour.  A  vertical  section  of 
veratrum  rhizome  is  also  very  characteristic,  and  more  especially  so 
from  presenting  a  fine,  dark,  wavy,  conically  arranged  line  running 
nearly  its  own  length,  and  thus  separating  the  outer  from  its  central 
portion.     No  such  wavy  line  is  seen  in  valerian  rhizome. 

Fourthly,  the  roots  of  veratrum,  which  arise  from  the  upper  part 
of  the  rhizome  only,  are  of  a  paler  colour  externally  than  those  of 
valerian  rhizome  ;  they  are  also  commonly  larger  and  more  shrivelled. 

Fifthly,  the  taste  of  veratrum  rhizome  and  roots  is  at  first  sweet, 
then  bitter,  acrid,  and  somewhat  numbing  ;  while  the  similar  parts 
of  valerian  have  no  acridity,  but  are  evidently  aromatic  and  some-* 
what  bitter. 


MATERIA    MEDICA.  1G9 

Sixthly,  the  veratrum  in  itself  has  no  marked  odour,  and  although 
by  its  admixture  with  valerian  root  it  has  acquired  the  peculiar 
odour  of  that  drug,  it  is  feeble  when  compared  with  valerian  itself. 
The  veratrum  rhizome  also  excites  sneezing  when  cut  or  bruised,  as 
found  by  its  action  in  making  sections  to  examine  its  structure. 

There  is  one  chemical  distinctive  character,  which  is  so  marked, 
and  at  the  same  time  so  simple  and  readily  observed,  that  it  will  be 
useful  to  notice  it.  It  is  derived  from  the  application  of  sulphuric 
acid  to  a  transverse  or  vertical  section  of  the  two  rhizomes.  Thus, 
if  the  acid  be  added  to  a  section  of  white  hellebore,  a  deep  orange 
yellowish  red  colour  is  at  once  produced  from  its  action  on  the  con- 
tained alkaloids,  which  soon  changes  to  a  dark  blood  red ;  but  its 
application  to  a  section  of  valerian  is  simply  to  heighten  the  natural 
colour  of  that  drug. 

The  sample  of  valerian  root  which  forms  the  subject  of  this 
paper  weighed  exactly  forty-two  ounces,  of  which  thirty- four  ounces 
were  true  valerian,  and  eight  ounces  white  hellebore  rhizome ;  so 
that  the  serious  nature  of  the  admixture  may  be  seen  at  once.  The 
sample  also  contained  a  few  pieces  of  veratrum  rhizome  without  any 
trace  of  leaves,  but  with  the  roots  still  attached  ;  such  pieces  have  of 
course  a  much  greater  resemblance  to  valerian  root,  but  they  can  be 
readily  distinguished,  with  ordinary  care,  by  the  different  appear- 
ances presented  on  making  a  transverse  or  vertical  section  of  the 
two  rhizomes,  and  by  the  action  of  sulphuric  acid. 

Although  it  was  impossible  to  determine  with  absolute  certainty 
the  species  of  veratrum  from  the  specimen  of  rhizome  under  exami- 
nation, the  author  has  but  little  doubt  that  it  was  from  some  form 
of  Veratrum  album,  and  that  both  it  and  the  valerian  rhizome  were 
gathered  together. 

Helianthus  Annuus.  {Neio  Remedies,  from  Archiv  der  Pharmacie, 
1876.)  The  cultivation  of  the  sunflower  {Helianthus  annuus)  is 
carried  on  extensively  in  some  countries,  as  central  Russia  and 
Hungary,  chiefly  for  obtaining  the  oil  of  the  seeds,  which  forms  an 
excellent  salad-oil,  while  the  residuary  cakes  find  employment  as 
food  for  cattle. 

The  yield  is  so  large  and  the  labour  connected  with  its  cultivation 
so  trifling,  that  it  deserves  the  attention  of  agriculturists.  Each 
acre  of  land  may  easily  contain  16,000  plants  without  at  all  inter- 
fering with  each  other.  Numerous  trials  have  shown  that  each 
fresh  plant  weighs  on  an  average  10|  pounds,  including  the  seeds, 
which  amount  to  about  half  a  pound.  The  yield  of  one  acre  may 
be  stated  as  80,000  lbs.  of  stems,  80,000  lbs.  of  leaves,  flowers  (ex- 


170  YEAR-BOOK    OF    PHARMACY. 

eluding  seeds),  and  roots,  and  8000  lbs.  of  seeds.  The  stems  and 
leaves  contain  a  considerable  amount  of  potassium  nitrate,  and  are 
therefore  easily  reduced  to  ash,  which  will  yield  to  water  about 
2300  lbs.  of  potash.  There  are  two  varieties  of  the  plant,  one  con- 
taining white,  and  the  other  black  and  white  seeds.  The  former 
contain  from  25  to  28  per  cent,  of  oil,  the  latter  from  16-25  to  26 
per  cent.  ;  but  the  amount  of  kernel  varies  in  the  two  sorts.  The 
average  yield  from  100  parts  of  kernel  is  about  44<6  per  cent,  of 
oil.  But  it  must  be  understood  that  this  percentage  is  the  actual 
amount  existing  in  the  seeds,  and  extracted  with  ether.  In  practice, 
especially  when  pressure  alone  is  resorted  to,  the  actual  yield  will 
be  somewhat  less.  Analysis  of  the  ash  of  the  plant  (excepting  the 
seeds)  yielded  the  following  results ;  the  corresponding  figures 
obtained  from  an  analysis  of  the  ash  of  the  seeds,  are  added  after 
each  constituent  in  brackets  : — potash,  47-687  (14-475)  ;  soda,  1-092 
(6-119);  lime,  O'S-dI  (6-811);  magnesia,  5-291  (1-0960);  alumina, 
0-280  (0-227)  ;  ferric  oxide,  0-170  (1-427)  ;  chlorine,  5-004  (2-162) ; 
sulphuric  acid,  1-344  (2-086);  phosphoric  acid,  6-968  (31-848); 
silica,  0-687  (10-811)  ;  carbonic  acid,  21-626  (13-074). 

Researches  on  Mancona  Bark.  K  Grallois  and  E.  Hardy. 
(Journal  de  Pharmacie  ct  de  Chimie,  July,  1876,  25.)  The  Erythro- 
phloeum  Guineense  (sassy  tree,  or  red- water  tree)  is  a  tall  tree  gro-w- 
ing  along  the  West  Coast  of  Africa,  and  belonging  to  the  order 
Leguminosce.  A  previous  notice  of  its  bark  will  be  found  in  the 
Year-Booh  of  Pharmacy,  1876,  p.  246.  The  bai'k  is  used  by  the 
natives  for  poisoning  arrows  and  preparing  ordeal  liquors  for  crimi- 
nals. By  the  following  process  the  authors  have  isolated  from  it 
a  crystalline  alkaloid  possessing  marked  poisonous  properties  : — 

The  finely  powdered  bark  was  macerated  for  three  days  with 
alcohol  of  90  per  cent,  slightly  acidulated  with  hydrochloric  acid, 
the  tincture  pressed  off  and  the  residue  subjected  to  second,  and 
afterwards  to  a  third,  maceration  in  the  same  way.  After  filtering 
the  united  tinctures,  the  greater  part  of  the  alcohol  was  recovered  by 
distillation  from  a  water  bath,  and  the  remainder  evaporated  at  a 
low  temperature.  A  reddish-brown  extract  was  thus  obtained,  rich  in 
resinous  matter.  This  was  treated  five  or  six  times  with  lukewarm 
distilled  water,  and  tlie  liquor  cooled,  filtered,  and  evaporated  on  a 
water  bath.  When  suitably  concentrated  it  was  again  allowed  to 
cool,  decanted,  saturated  with  ammonia,  and  poured  into  four  or 
five  times  its  volume  of  acetic  ether,  from  which  any  acid  present 
had  been  previously  removed.  After  shaking  several  times  the  ether 
was  removed  by  means  of  a  funnel  having  a  stopcock.    The  aqueous 


MATERIA    MEDICA.  171 

solution  was  then  exhausted  a  second  time  with  four  times  its  volume 
of  acetic  ether.  The  ethereal  solutions  were  filtered,  evaporated  on 
a  "water  bath  at  a  low  temperature,  and  the  yellowish  residue  treated 
several  times  with  cold  distilled  water.  The  aqueous  solution  "was 
filtered  and  allowed  to  evaporate  in  the  vacuum  of  an  air  pump. 
Another  process  employed  was  that  of  Stas,  with  the  substitution 
of  acetic  ether  for  ordinary  ether  after  the  saturation  with  carbonate 
of  soda. 

Erythrophleine  thus  obtained  is  a  colourless  crystalline  substance, 
soluble  in  "water,  alcohol,  acetic  acid,  and  amylic  alcohol ;  but  only 
slightly  soluble  in  ether,  benzol,  and  chloroform.  It  combines  with 
acids  to  form  salts.  With  potassium  permanganate  and  sulphuric 
acid  it  strikes  a  violet  colour,  less  intense  than  that  produced  by 
strychnine  under  the  same  conditions ;  the  colour  soon  changes  to 
a  dirty  brown.  Its  behaviour  with  the  usual  alkaloid  reagents  is  as 
follo"ws  : — 

Picric  acid  :  yellowish  green  precipitate. 
Iodine,  in  potassium  iodide  :  reddish  yello"w  precipitate. 
Iodide  of  mercury  and  potassium  :  "white  precipitate. 
Iodide  of  bismuth  and  cadmium  :  flocculent  white  precipitate. 
Potassium  bichromate  :  yellowish  precipitate. 
Mercuric  chloride  :  "white  precipitate. 
Auric  chloride  :  "whitish  precipitate. 
Palladic  chloride  :  "white  precipitate. 

The  assumption  that  erythrophleine  might  be  a  product  from  a 
natural  glucoside,  and  not  an  alkaloid  already  existing  in  the  drug, 
"was  shown  to  be  "untenable  by  tests  applied  directly  to  the  infu- 
sion, and  by  actual  separation  of  erythrophleine  "without  the  inter- 
vention of  an  acid. 

Physiological  experiments  made  by  the  authors  on  dogs  and  frogs 
show  that  erythrophleine  possesses  strong  toxic  properties,  and  indi- 
cate that  it  is  a  cardiac  poison.  Whilst  curare  retards  the  effects  of 
mancona  poison,  atropine  does  not  restore  the  movements  of  the 
heart  paralysed  by  it. 

ErythropliloetiTn  cotominga,  or  Jcoumanga,  is  also  a  considerable  tree 
of  the  same  genus.  All  its  parts  are  poisonous,  and  in  the  "way 
indicated  above  the  authors  have  separated  an  alkaloid  which  is 
closely  related  to  erythrophleine,  if  not  identical  with  it. 

Ava,  or  Kava-Kava.  (Pharm.  Journ.,  3rd  series,  vii.,  147.)  The 
root  known  under  the  name  of  kava-kava  has  lately  attracted  some 
attention  in  France  as  a  remedy  for  gonorrhoea,  and  will  probably 
be  tried  in  this  country.     It  "was  first  recommended  for  this  purpose 


172 


YEAR-BOOK    OF    PHARMACY. 


in  1857  ;  but  tliougli  notices  of  the  plants  yielding  it  (Piper  methy- 
sticum)  have  appeared  in  several  journals,  a  full  description  of  the 
root  and  leaf  for  the  pui'poses  of  pharmacognosy  does  not  appear  to 
have  been  given  in  any  of  the  reports  hitherto  published. 

The  ava,  or  kava-kava  plant,  is  cultivated  in  Viti,  Tahiti, 
HaT\'aii,  the  Society  and  Tongan  islands.  Several  varieties  of  the 
plant  are  distinguished  by  the  natives.  Those  which  grow  on  dry 
soil  are  said  to  produce  the  most  active  roots. 

The  Piper  methysticum  is  a  shrub  about  6  feet  high,  with  stems 
varying  from  1  to  It  inch  in  thickness.  The  leaves  are  rather 
large,  varying  in  size  from  4  to  8  inches  in  length,  and  being  nearly  as 
broad  as  they  are  long.  In  shape  they  are  cordate,  tapering  above 
somewhat  suddenly  into  a  very  short  acute  apex.  The  leaves  are 
stalked,  the  petiole  being  usually  from  1  to  H  inch  long,  and  dilated 
towards  its  base.  To  the  naked  eye  the  leaves  appear  smooth, 
although  with  the  aid  of  a  lens  they  are  seen  to  have  the  veins 
covered  with  minute  hairs,  while  the  rest  of  the  leaf  has  short  hairs 
thinly  scattered  over  it.  The  principal  veins  of  the  leaf,  of  which 
there  are  usually  ten  to  twelve,  radiate  from  the  top  of  the  petiole, 
the  three  central  veins  being  very  close  together  for  about  half  an 
inch  upwards  from  the  base  of  the  leaf. 

The  root  is  large  and  fibrous,  but  rather  light  and  spongy  in 
texture.  When  fresh,  it  is  said  to  weigh  usually  from  2  to  4  lbs., 
although  it  sometimes  attains  as  much  as  20  lbs.  in  weight,  or  even 
more.  In  drying,  however,  it  loses  rather  more  than  half  its  weight. 
Externally  the  root  is  of  a  greyish  brown  colour,  and  has  a  very 
thin  bark,  which  when  sliced  off  shows  a  complete  network  of 
woody  tissue,  some  of  the  interstices  of  which  are  filled  with  soft 
yellowish  white  cellular  matter,  whilst  others  are  quite  empty. 
Internally  the  root  is  of  a  yellowish  white  colour.  (In  a  variety  of 
the  plant  known  as  "  marea,"  it  is  citron  yellow  internally ;  and  in 
another  variety,  know  under  the  name  of  "  avini-ute,"  it  is  of  a 
pinkish  colour).  A  transverse  section  shows  a  number  of  narrow 
lines  (woody  bundles)  radiating  from  near  the  centre  to  the  circum- 
ference, the  portions  of  the  soft  cellular  tissue,  by  which  the  lines 
are  separated  from  each  other,  being  much  wider  than  the  lines 
themselves.  The  central  portion  of  the  root  is  soft  and  cellular, 
with  a  few  woody  bundles  anastomosing  with  each  other  and  pro- 
ceeding at  right  angles  to  the  radiating  bundles,  so  that  they  form 
a  network  in  the  centre  of  the  transverse  section.  The  root  has  a 
pleasant  odour,  recalling  that  of  the  lilac  (Syringa  vulgaris,  L.), 
or  meadow-sweet  (Bpiroea  ulmaria,  L.).     It  has  a  slightly  pungent 


MATERIA   MEDICA.  173 

taste,  and  causes  an  increase  in  the  flow  of  saliva,  with  a  slightly 
astringent  sensation  in  the  month,  and  a  scarcely  perceptible  bitter- 
ness. The  root  and  extreme  .base  of  the  stem  are  the  parts  gener- 
ally used. 

The  form  in  which  it  has  been  used  for  medicinal  purposes  is  an 
infusion  made  by  macerating  about  one  dram  of  the  scraped  root 
in  a  quart  of  water  for  five  minutes.  Unlike  most  other  remedies 
for  gonorrhoea,  the  taste  of  the  infusion  is  pleasant,  while  its  bitter- 
ness  improves  the  appetite  and  does  not  produce  nausea.  The  root 
contains,  according  to  M.  Cuzant,  an  essential  oil  of  a  pale  yellow 
colour,  2  per  cent,  of  an  acrid  resin,  and  about  1  per  cent,  of  a 
neutral  crystalline  principle  called  kavahin  or  methysticin,  which  is 
obtained  in  acicular  crystals  by  crystallization  from  a  concentrated 
tincture.  Kavahin  differs  from  piperine  and  cubebin  in  being 
coloured  red  by  hydrochloric  acid — the  red  colour  fading  on  exposure 
to  air  into  a  bright  yellow,  and  in  being  coloured  by  strong  sul- 
phuric acid  a  purplish  violet  colour,  which  passes  into  green.  The 
root  contains  also  nearly  half  its  weight  of  starch. 

The  action  of  kava  root  appears  to  vary  with  the  amount  taken. 
In  small  doses  it  is  generally  stated  to  act  as  a  stimulant  and  tonic; 
but  when  taken  in  large  doses  it  produces  an  intoxication,  which 
differs  from  that  caused  by  alcohol  in  being  of  a  silent  and  drowsy 
nature,  accompanied  by  incoherent  dreams,  the  drinker  not  being 
quarrelsome  or  excited.  The  roots  grown  in  damp  soil,  howevei', 
produce  a  slightly  different  effect,  the  drunken  person  becoming 
irritated  by  the  least  noise. 

It  appears  probable  that  the  medicinal  properties  of  the  plant  are 
due  neither  to  kavahin  nor  to  the  resin,  since  a  watery  infusion 
produces  the  characteristic  effects  of  the  drug ;  and  neither  kavahin 
nor  the  resin  are  soluble  in  water.  The  therapeutical  properties  of 
the  different  chemical  constituents  of  the  root,  therefore,  still  require 
more  accurate  investigation. 

The  root  is  stated  to  have  been  used  with  success  in  erysipelatous 
eruptions  (Pharm.  Journ.  [1],  ix.  218),  which  is  rather  remarkable, 
since,  when  taken  in  excess  as  an  intoxicating  beverage,  it  produces 
a  pecu.liar  kind  of  skin  disease,  called  in  Tahiti,  "  arevarea."  In 
old  drinkers  the  vision  becomes  obscure,  and  the  skin,  especially  in 
parts  where  it  is  thick,  becomes  dry,  scaly,  cracked,  and  ulcerated. 
In  Nukahivi  the  natives  use  kava  for  phthisis  and  in  bronchitis,  a 
small  dose  being  taken  at  bed  time.  It  has  also  been  recommended 
to  be  used  internally  and  locally  for  gout  (Medical  Times  and 
Gazette,  Dec,  1854,  591).      A  figure  of  the  plant  and  of  sections 


174  TEAR-BOOK    OF    PHARMACY. 

of  the  root  ■will  be  found  in  the  Pharmaceutical  Journal,  pp.  149, 
150. 

Simn  Latifolium,  Gray.  A.  R.  Porter.  {American  Journ.  of 
Pharm.,  August,  1876.)  Slum  latifolium,  an  umbelliferous  plant, 
growing  in  California  and  along  the  Pacific  coast,  in  damp  and 
marshy  places,  commonly  known  as  wild  parsnip,  was  brought  to 
tlie  notice  of  the  people  there,  about  three  years  ago,  by  a  man  being 
poisoned  by  eating  some  of  the  root. 

Sium  latifolium  has  a  short,  upright  root-stock,  varying  in  size 
from  one-half  to  two  inches  or  more  in  length,  and  about  the  same 
in  diameter,  so  it  becomes  almost  spherical  in  outline ;  bases  of 
leaves  are  still  attached  to  the  crown.  It  presents  a  very  rough, 
wrinkled  appearance,  and  is  of  a  grey  or  yellowish  brown  colour. 
It  branches  at  once  into  a  number  of  large  roots,  from  four  to 
twelve,  and  even  more.  These  are  of  the  same  colour,  from  ^  to  i 
or  f  inch  in  thickness,  and  2  to  6  inches  long,  very  much  wrinkled 
longitudinally,  somewhat  flattened  and  contorted,  and  nearly  uni- 
form in  thickness.  On  soaking  in  water  they  become  about  twice 
as  large.  The  dried  root  breaks  with  a  very  short  fracture,  is  white 
inside,  with  a  yellowish,  spongy  meditullium  and  numerous  resin 
cells,  which  are  plainly  visible  with  the  naked  eye,  scattered  irregu- 
larly throughout  the  bark.  The  root  has  rather  an  agreeable  aro- 
matic odour,  and  a  sweetish,  aromatic  and  somewhat  pungent  taste. 

In  attempting  to  separate  the  proximate  principles  of  the  root, 
an  alcoholic  tincture  was  made,  concentrated  and  precipitated  by 
water.  In  the  clear  aqueous  solution, Trommer's  test  indicated  the 
presence  of  much  sugar,  besides  some  colouring  matter.  The  pre- 
cipitated oleo-resin  was  distilled  with  water,  the  distillate  containing 
some  volatile  oil,  which  was  colourless,  and  had  the  aromatic  odour 
and  warm,  pungent  taste  of  the  root.  The  soft  residue  was  sepai"ated 
by  hot  petroleum  benzin  into  a  fixed  oil  and  resiji.  The  oil  was 
thick,  deep-red,  of  a  slight  odour  and  disagreeable  taste,  soluble  in 
alcohol,  chloroform,  ether,  oil  of  turpentime,  benzin,  and  carbon 
bisulphide. 

The  resin  was  easily  rubbed  into  a  reddish  brown  powder,  which 
had  a  very  slight  odour  and  but  little  taste  ;  fusible  when  heated, 
and  uncrystallizable ;  soluble  in  alcohol,  chloroform,  and  ether;  in- 
soluble in  benzin  and  bisulphide  of  carbon.  This  resin  appears  to 
be  the  poisonous  principle,  since  a  small  portion  of  it  given  to  a  cat 
produced,  in  the  course  of  two  hours,  frothing  at  the  mouth,  con- 
siderable pain,  and  then  convulsions,  from  which,  however,  the  cat 
recovered.     The  resin  was  not  quite  pure,  since  caustic  potash  dis- 


1 


MATERIA    MEDICA,  175 

solved  ouly  a  part,  leaving  a  portion  insoluble,  and  not  fusible  by 
heat.  The  root  exhausted  by  alcohol  was  found  to  contain  gum, 
albumen,  and  pectin,  but  no  starch. 

An  alkaloid  having  been  searched  for  with  negative  result  in  the 
alcohol  tincture,  a  decoction  of  the  root  was  distilled  with  caustic 
potash.  The  distillate  had  an  alkaline  reaction,  and  its  odour  re- 
minded of  that  of  conium  ;  but  when  neutralized  with  an  acid,  the 
distillate  was  neither  precipitated  by  tannin  nor  by  iodohydrargy- 
rate  of  potassium ;  it  was  probably  ammonia  contaminated  with 
some  odorous  product  of  decomposition. 

Slum  Latifolium.  N.  Rogers.  (Amer.  Journ.  Phann.,l^ov.,lS76.) 
The  water  parsnip  is  an  aquatic  plant  very  common  in  the  swamps 
and  along  the  water-courses  of  the  valleys  of  the  Pacific  slope.  Its 
root  is  creeping ;  stem  erect,  angular ;  leaf  pinnate ;  leaflets  ovate, 
lanceolate,  sessile,  smooth,  serrate,  sometimes  pinnatifid ;  flowers 
white,  large-rayed ;  involucres  many-leaved  ;  umbels  terminal. 

The  leaves  of  the  plant,  when  found  growing  in  water,  are  gener- 
ally bipinnatifid.  In  appearance,  growth,  odour,  and  taste  it  is 
closely  allied  to  its  innocent  congener,  the  Pastinaca  sativa.  On 
account  of  this  resemblance  it  has  frequently  been  productive  of 
dangerous  results,  when  eaten  through  mistake  for  the  harmless 
and  nutritious  root  of  that  edible  species. 

The  root  being  considered  the  most  active  part  of  the  plant,  it 
was  deemed  proper  to  subject  that  to  a  chemical  examination. 

A  portion  of  the  root  cut  up  fine  was  introduced  into  boilino- 
water  contained  in  a  retort,  and  a  volatile  oil  obtained,  which  had 
a  light  straw  colour,  neutral  reaction,  and  possessed  a  puno-ent 
odour,  resembling  somewhat  the  peculiar  odour  of  carrots.  A  cold 
infusion  of  the  fresh  root,  acidulated  with  hydrochloric  acid  and 
filtered,  to  separate  a  precipitate,  failed  to  give  a  precipitate  with 
iodohydrargyrate  of  potassium ;  but  when  distilled  with  an  excess 
of  potash  solution,  a  perfectly  clear  and  colourless  distillate  was 
obtained,  possessing  a  strong  alkaline  reaction  and  peculiar  mouse- 
like odour,  somewhat  similar  to  that  of  conium  ;  after  neutralization 
with  hydrochloric  acid,  however,  not  the  slightest  precipitate  was 
occasioned  by  pliosphomolybdic  acid,  iodohydrargyrate  of  potassium 
or  potassium  cadmic  iodide. 

The  neutralized  distillate  was  next  concentrated  on  a  water  bath 
and  then  allowed  to  evaporate  spontaneously  over  sulphuric  acid 
which  resulted  in  the  deposition  of  long,  slender,  colourless  needle- 
shaped  crystals.  On  the  addition  of  milk  of  lime,  a  peculiar  alka- 
line volatile  principle  was  instantly  liberated  from  its  combination 


176  TEAR-BOOK   OP    PHARMACY. 

and  distinctly  recognised  by  its  disagreeable  mouse-like  odour,  and 
the  property  of  restoring  the  blue  colour  to  reddened  litmus. 

Following  Wittstein's  process  for  preparing  pastinacina,  the  alka- 
line distillate  was  freed  from  the  volatile  oil,  neutralized  with 
sulphuric  acid,  evaporated,  and  treated  with  etherized  alcohol  to 
remove  ammonium  sulphate;  the  filtrate  evaporated  to  a  syrupy 
consistency,  and  distilled  with  solution  of  potash,  gave  a  distillate 
which  possessed  an  alkaline  reaction,  a  urinous  odour,  and  a  pungent 
taste.  After  neutralizing  with  sulphuric  acid,  needle-shaped  crystals 
were  obtained.     This  allcaloid  appears  to  be  analogous  to  pastinacina. 

A  spirituous  tincture  of  the  root  was  mixed  with  water,  and  the 
alcohol  and  volatile  oil  distilled  ofi*;  the  dark  reddish  brown  resin 
removed  from  the  aqueous  liquid  was  soluble  in  ether  and  alcohol, 
and  produced  in  the  throat  an  unpleasant  burning  sensation. 
"Weak  ammonia  dissolved  from  this  two  acid  resins,  which  were  pre- 
cipitated,— the  one  by  acetate,  the  other  by  subacetate,  of  lead.  The 
portion  insoluble  in  ammonia  consisted  in  part  of  an  indifferent 
resin.  It  was  dissolved  in  alcohol,  precipitated  by  a  spirituous 
solution  of  lead  acetate,  the  precipitate  decomposed  by  sulphuretted 
hydrogen,  and  the  sulphide  of  lead  treated  with  boiling  alcohol, 
from  which,  on  cooling,  shining  colourless  needles  of  a  neutral 
principle  separated,  which  were  insoluble  in  pure  and  acidulated 
water,  but  soluble  in  ether,  and  from  platinum  foil  volatilizable 
without  charring.  The  aqueous  filtrate  from  the  resin  obtained 
above  was  evaporated,  and  the  residue  incinerated ;  the  ashes 
contained  salts  of  potassium,  sodinm,  calcitom,  and  marjnesium.  On 
texamining  a  section  of  the  root  under  the  microscope,  starch  granules 
we  found  to  be  quite  plentiful  around  the  medullary  sheath  and 
near  the  cortical  portion.  They  polarized  but  feebly,  were  oblong, 
different  in  size,  and  quite  small.  Sugar,  albumen,  and  gum  were 
found  in  the  cold  infusion  by  appropriate  tests. 

Medical  Effects. — From  experiments  made  iipon  dogs,  the  volatile 
alkali  and  the  neutral  crystallizable  principle  were  both  found  to  be 
perfectly  inert ;  while  the  resinous  mass,  in  ten-grain  doses,  was 
found  to  lessen  the  frequency  and  the  force  of  the  heart's  beat, 
producing  also  dizziness,  vomiting,  and  purging,  with  slight  con- 
vulsive movements.  These  poisonous  symptoms  having  gradually 
disappeared,  the  animals  were  left  in  a  prostrate,  weakeued  con- 
dition, from  which  they  slowly  recovered. 

Arrowroot.  T.  Greenish.  (P^a/-»i.  Jfj^tr/t.,  3rd  series,  vii.,  169.) 
The  origin  of  the  term  arrowroot  is  involved  in  some  obscurity, 
and  its  application   to  the   starch  derived  from   the   maranta   to 


MATERIA    MEDICA.  177 

the  exclusion  of  that  from  every  other  source  may  be  called  in 
question. 

It  is  generally  admitted  that  the  manihot,  which  yields  the  starch 
known  as  cassava  starch,  is  a  native  of  Brazil ;  if,  therefore,  the 
maranta  be  an  introduced  plant,  which  agrees  with  common  report, 
the  probability  is  that  the  term,  "  ara-ruta,"  which  is  unquestionably 
a  native  Indian  word,  originally  applied  to  one  or  more  varieties  of 
the  manihot ;  and  if  so,  cassava  starch  has  certainly  equal  claims 
with  the  maranta  to  the  more  popular  and  commercial  name  "  arrow- 
root." The  Manihot  utilissima,  Pohl.,  yields  the  cassava  starch 
of  commerce ;  it  is  also  that  used  in  the  manufacture  of  tapioca. 

Another  variety  of  manihot  yields  a  starch  having  a  little 
colour ;  this  is  kept  for  home  consumption.  The  author  thinks 
it  probable  that  at  different  periods,  when  a  starch  has  been  found 
capable  of  preparation  so  as  to  become  an  acceptable  article 
of  diet,  the  term  "  arrowroot "  has  been  applied  to  it ;  and  thus  we 
have  other  starches  which  have  long  been  designated  by  the  name 
of  arrowroot. 

Brazilian  arrowroot  (manihot). 

Tahiti  arrowroot  (tacca). 

Portland   arrowroot  (arum). 

East  India  arrowroot  (curcuma). 

Some  of  these  are  rarely,  if  ever,  found  in  commerce,  although 
extensively  used  in  the  countries  where  they  are  produced. 

The  cassava  starch  has  been  found  on  several  occasions  mixed 
with  that  of  maranta,  and  sold  as  arrowroot.  One  such  case  has 
been  reported  by  Dr.  Muter,  and  another  by  Mr.  Jones,  of  Birming- 
ham. It  is  beyond  question  that  for  some  time  marantas  have  been 
imported  into  this  country  adulterated  with  cassava.  The  author  has 
several  times  detected  it  as  an  adulterant  of  pepper,  and  has  also 
found  it  mixed  with  a  maranta,  but  had  no  means  of  ascertaining 
whether  this  arrowroot  was  "  as  imported,"  or  had  been  tampered 
with  in  this  country. 

The  starch  of  the  manihot,  commonly  called  cassava  starch,  is 
one  with  which  every  pharmacist  who  has  a  microscope  (and  no 
pharmacy  is  complete  without  one)  should  be  familiar.  The  accom- 
panying woodcut  shows  the  usual  forms  of  this  starch. 

They  are  for  the  most  part  muller- shaped,  with  a  fair  sprinkling 
of  the  circular ;  some  of  the  muller-shaped  have  truncate,  others 
dihedral  bases.  If  the  starch  be  examined  in  situ,  as  in  the  meal 
of  the  cassava,  there  will  be  found  a  good  many  doublets  and 
triplets  as  shown  in  the  drawing ;  but  these  combinations  are  rarely 


178 


TEAR-BOOK   OF   PHARMACY. 


present  in  a  commercial  sample  of  the  prepared  starcli.  The  separa- 
tion of  the  grains  composing  the  doublet  gives  the  muUer-shaped 
truncated  granules,  and  that  of  the  triplet  the  muller-shaped  with 
dihedral  bases.  The  diameter  of  the  granules  ranges  from  0008  to 
0-022  mm. 

A  very  interesting  and  instructive  experiment,  with  the  view  of 
determining  the  true  forms  of  these  grains  to  which  the  names 
muller-shaped  and  circular  are  given,  may  be  witnessed  with 
advantage.  After  having  examined  under  the  microscope  a  little  of 
the  starch,  using  as  a  medium  a  mixture  of  spirit,  water,  and 
glycerin,  the  single  forms  here  given  will  for  the  most  part  be  seen 
in  the  field  of  the  microscope.  If  now  a  drop  of  alcohol  be  placed 
on  the  edge  of  the  covering  glass,  capillary  attraction  will  cause  it 


to  run  in  rapidly,  and  in  its  course  the  grains  will  be  rolled  over 
several  times.  It  will  be  observed  that  a  granule  which  appears 
muller-shaped  when  seen  from  the  side,  with  the  neuclus  indicated 
by  a  spot  or  a  fissure  a  little  out  of  the  centre,  or  eccentric,  when 
rolled  over  so  as  to  be  seen  with  its  crown  towards  the  observer, 
appears  circular ;  also  that  one  of  the  triplet  grains  with  a  dihedral 
base,  when  seen  with  its  base  uppermost  will  give,  with  other  grains 
having  polyhedral  bases,  those  angular  forms  of  which  the  drawing 
indicates  one  or  more  examples.  Careful  illumination  will  occasion- 
ally show  one  or  two  zones  indicating  the  lamination  of  the  grain. 
If  when  the  grains  have  ceased  to  revolve,  another  drop  of  spirit  be 
applied  to  the  opposite  side  of  the  covering  glass,  the  movement 
will  be  repeated. 


MATERIA    MEDICA. 


179 


The  starch  of  the  tacca,  called  Tahiti  arrowroot,  is  one  resembling 
that  of  the  cassava,  but  it  is  rarely  found  in  commerce ;  the  muller- 
sliaped  granules  are,  however,  larger,  and  there  are  not  proportion- 
ately so  many  circular  ones.  The  diameter  ranges  from  0'026  to 
0-045  mm. 

The  only  other  starch  of  this  form  is  that  of  the  Castanospermum 
Australe,  or  Moreton  Bay  cbestnut.  It  was  shown  at  the  Paris 
exhibition  ;  but  from  that  time  to  the  present  it  bas  not  appeared  as 
a  commercial  article,  so  that  it  is  not  likely  by  its  presence  to  com- 
plicate matters,  or  embarrass  the  observer. 

The  author  believes  that  all  the  cassava  of  commerce  is  the  pro- 
duce of  Maniliot  tdilissima,  Pohl. 

The  Quinine  Flower.  D.  Palmer.  {Araer.  Journ.  Pharm, 
October,  187G.)  The  quinine  flower  is  an  annual  from  twelve  to 
eighteen  inches  high,  has  an  erect  green  stem,  linear  leaves  of  about 
one-half  to  an  inch  in  length,  and  small  white  flowers.  The  root 
consists  of  numerous  slender  fibres. 

It  is  a  native  of  Florida,  and  is  found  most  abundantly  in  flat 
pine  woods,  in  a  moderately  dry  soil,  making  its  appearance  in 
March  or  April,  and  flowering  from  July  to  September.  The 
specimens  furnished  me  were  gathered  three  or  four  miles  south  of 
Monticello,  in  Jefferson  county.  In  the  lower  portions  of  the 
county  it  is  very  abundant,  and  is  successfully  employed  by  those 
living  in  its  vicinity  for  the  cure  of  different  types  of  malarious 
fever,  the  whole  plant  being  used,  either  in  the  form  of  decoc- 
tion or  extract,  and  given  ad  lihitum  or  until  the  patient  feels  the 
effects  of  quinine  in  his  head.  It  is  a  curious  fact  that  persons 
brought  under  the  influence  of  this  remedy  experience  similar  sensa- 
tions— such  as  tension  or  fulness  in  the  head,  ringing  in  the  ears  or 
partial  deafness — as  when  under  the  influence  of  quinia,  and  hence 
its  name.  Its  reputation  as  an  antiperiodic  was  established  during 
the  late  civil  war,  when,  owing  to  the  scarcity  of  quinine,  every 
opportunity  was  offered  for  testing  the  relative  value  of  various 
substitutes. 

The  quinine  flower  is  intensely  and  permaneritly  bitter,  yielding 
its  properties  to  water  and  alcohol.  A  saturated  tincture  in  doses 
of  one  teaspoonful  every  two  hours  was  found  suSicient  to  break 
the  paroxysm  of  intermittent  fever.  Larger  quantities  may  be 
given  in  obstinate  cases,  or  in  the  remittent  form  of  the  disease. 

To  the  foregoing  the  following  remarks  are  added  by  the  Editor 
of  the  American  Journal  of  Pharmacy  : — 

At  our  request  Dr.  Palmer  bas  sent  us  some  of  the  flowering 


180  TEAR-BOOK   OF    PHARMACY. 

plants  referred  to  in  the  preceding  paper.  The  plants  are  found  to 
belong  to  the  natural  order  of  Gentianaccp,  and  to  the  sub-order 
GentianecB,  having  the  corolla  lobes  twisted  (contorted)  in  the  bud ; 
the  distinct  style  being  deciduous,  it  must  be  placed  into  the  section 
to  Tvhich  Erythroea  and  Sahbatia  belong.  Its  botanical  characters 
agree  with  those  of  the  last-named  genus,  and  more  particularly 
with  the  group  which  has  the  white  or  purplish  flowers  scattered  on 
alternate  penduncles,  and  the  corolla  five-parted. 

On  comparing  it  with  the  American  species  in  the  college 
herbarium  of  Dan.  B.  Smith,  it  was  found  to  correspond  with  a 
specimen  of  Sabbatia  ElUoUli,  Steud.,  which  is  marked  ex  lierbar. 
Chapmani.  This  plant  is  described  in  Chapman's  "  Flora  of  the 
Southern  United  States,"  as  follows  : — 

''  Stem  low,  terete,  paniculately  much  branched  from  near  the 
base,  the  branches  diffuse  ;  leaves  small,  sessile,  the  lowest  obovate, 
the  upper  linear ;  lobes  of  the  corolla  three  to  four  times  as  long  as 
the  short  filiform  calyx-lobes.  (S.  paniculata,  Ell.)  Open  pine 
barrens,  Florida  to  South  Carolina.  August  and  September. — 
Stems,  I  to  1|  foot  high ;  leaves,  from  3  to  6  inches  long ;  corolla, 
8  to  10  lines  wide." 

In  both  the  herbarium  specimen  and  the  plants  sent  by  Dr. 
Palmer,  the  calyx  lobes  are  more  prominent  than  might  be  supposed 
from  the  description  given ;  but  they  are  evidently  described  as 
short,  in  comparison  with  the  much  longer  calyx  lobes  of  Sabbatia 
stellarus,  gracilis  and  allied  species,  in  which  they  are  about  equal 
in  length  to  the  corolla,  whilst  in  the  species  under  consideration 
they  are  about  one-third  the  length.  The  lowest  leaves  are  obovate, 
those  a  little  higher  on  the  stem  obolanceolate  with  an  acute  point, 
and  become  rapidly  narrowed  to  a  linear  shape.  The  stems  of  the 
plants  recently  received  are  from  20  to  24  inches  in  height,  and 
consequently  rather  exceed  the  height  given  by  Chapman. 

The  herb  has  at  first  an  herbacious  taste,  which  gradually 
develops  into  a  pure  and  persistent  bitter,  free  from  astriugency. 

The  popular  name  quinine  flower  appears  to  be  confined  to  a  small 
locality,  probably  to  only  a  portion  of  Florida.  Porcher's  "Re- 
sources of  the  Southern  Fields  and  Forests,"  p.  ttiJG,  however, 
mentions  Gentiana  quimjeflora  under  the  names  of  Indian  quinine 
and  Ague  weed,  and  states  that  "this  and  the  G.  saponaria  are 
esteemed  fully  equal  to  the  important  gentian ;  in  large  doses  they 
are  said  to  be  laxative ;  Dr.  E.  P.  Wood,  of  Wisconsin,  has  given 
this  plant  with  success  in  intermittent  fever."  He  also  gives  a 
detailed  account  of  the  medicinal  properties  of  Sabbatia  angularis, 


MATERIA    MEDICA.  181 

the  American  centaury,  and  states  that  8.  stellarus  and  S.  gracilis 
possess  properties  similar  to  the  former. 

This  genus  of  North  American  plants  is  closely  allied  to  Erythrcea, 
of  which  several  species  (E.  chilensis,  E.  centaurium,  E.  linarifolla, 
etc.)  are  still  employed  in  different  countries  as  tonics,  and  some- 
times as  antiperiodics ;  but  we  do  not  remember  that  effects 
resembling  quininism  have  been  ascribed  to  any  of  those  plants, 
such  as  Dr.  Palmer  states  are  experienced  from  the  quinine  flower 
of  Florida. 

Antiseptic  Properties  of  the  Root  of  Rubia  Tinctonun.  M. 
Rostaing.  (Comptes  Rendiis,  Ixxxii.,  551.)  The  author  observed 
that  a  piece  of  meat  placed  in  a  jar  containing  powdered  madder 
root  kept  perfectly  good  for  seven  months,  during  which  time  the  jar 
was  opened  at  least  a  dozen  times.  It  had  merely  lost  its  moisture, 
its  weight  having  decreased  from  119  grams  to  25  grams;  but  there 
was  not  the  slightest  sign  of  decomposition.  He  therefore  recom- 
mends madder  for  the  preservation  of  corpses  and  the  disinfection 
of  burial  grounds. 

Ergot  in  Atony  of  the  Bladder.  Prof.  Langenbeck.  (Netv 
Bern.,  1877,  207.)  The  author,  at  a  meeting  of  the  Berlin  Medical 
Society,  stated  that  in  atony  of  the  bladder,  associated  with  enlarged 
prostate,  in  elderly  men,  in  which  the  organ  is  never  completely 
emptied  of  urine,  he  had  lately  tried  the  hypodermic  injection  of 
ergotin  with  most  surprising  results.  In  three  cases  the  contractile 
power  of  the  bladder  was  at  once  increased  so  as  to  enable  the 
patient  to  discharge  additional  urine,  and  in  a  few  days  it  had  so 
augmented  that  very  little  urine  was  left  behind.  After  one  or  two 
injections  the  improvement  was  considerable,  and  even  a  diminution 
in  the  size  of  the  prostate  seemed  to  have  ensued.  Dr.  Israel  said  that 
he  had  derived  the  same  benefit  from  the  employment  of  ergotin, 
and  referred  to  the  case  of  a  patient  who  was  thus  enabled  to  hold 
his  water  for  three  hours,  whereas  before  he  voided  it  every  ten 
minutes. 

Persian  Insect  Powder.  R.  Rother.  (Druggists'  Circular  and 
Gheriiical  Gazette,  July,  1876.)  The  powdered  flowers  of  Pijrethrum 
caucasicum,  roseum,  etc.,  have  in  the  course  of  years  attained  cele- 
brity as  an  insecticide. 

The  non-poisonous  character  of  the  powder  widens  its  range  of 
application  to  an  unlimited  extent,  and  places  it  prominently  above 
the  numerous,  often  highly  poisonous  substances  used  for  the  same 
purposes.  Its  general  use  has,  however,  been  restricted  by  reason 
of  its  costliness. 


182  YEAR-BOOK   OF    PHARMACY, 

Persian  insect  powder  is  analogous  in  its  action  to  Coccuhis  indicus. 
Its  contact  promptly  stupefies,  and,  if  prolonged,  death  rapidly  en- 
sues. It  appears  to  be  harmless  to  the  larger  animals,  but  if  much 
of  its  dust  is  inhaled,  dizziness  will  result.  That  the  substance  must 
possess  medicinal  virtues  cannot  be  questioned,  and  probably  before 
loug  will  be  largely  employed  otherwise  than  as  a  vermin  destroyer. 
The  powder  has  never  been  thoroughly  investigated.  It  was  found 
not  to  contain  an  alkaloid  nor  santonin,  so  that  its  virtues  were 
ascribed  to  the  volatile  oil  it  contains.  Early  last  summer,  the  author 
made  a  preliminary  examination  of  it,  and  by  operating  upon  3500 
grains  of  the  powder,  obtained  results  which  were  recently  confirmed 
by  a  second  experiment  upon  20  ounces  of  the  material ;  but  an 
altogether  thorough  investigation  was  cut  short  by  an  accident, 
through  which  most  of  the  material  was  lost. 

The  author  found  that  an  aqueous  percolate,  as  also  an  aqueous 
ammoniacal  one,  when  treated  with  chloroform,  ether,  and  benzine, 
gave  no  indications  of  an  alkaloid  soluble  in  these  liquids.  Three 
acid  bodies  were,  however,  isolated.  An  oleo-resinous  greenish 
yellow  acid,  which  the  author  denominates  "  persicein,"  was  found, 
having  the  odour  of  the  powder,  and  its  sub-bitter  taste.  It  is, 
however,  not  the  active  principle  of  the  plant.  This  acid  resin  is 
soluble  in  ether,  alcohol,  and  benzine,  but  insoluble  in  chloroform  ; 
it  is  instantly  dissolved  by  ammonia  and  the  fixed  alkalies,  from 
which  acids,  in  not  too  dilute  solutions,  precipitate  it  milky  white. 
It  is  somewhat  soluble  in  water,  imparting  a  greenish  yellow  colour, 
and  its  characteristic  odour  and  bitter  taste.  It  forms  insoluble 
salts  with  the  heavy  metals. 

A  second  acid  was  found ;  it  has  a  light  brown  colour,  and  is 
nearly  insoluble  in  cold  water,  slightly  soluble  in  hot.  It  is  soluble 
in  alcohol  with  a  red-brown  colour,  but  insoluble  in  chloroform, 
ether,  and  benzine ;  water  reprecipitates  it  from  the  alcoholic  solu- 
tion. It  forms  soluble  salts  of  dark  brown-red  colour  with  ammonia 
and  the  fixed  alkalies ;  acids,  again,  precipitate  it  from  the  solutions 
of  its  salts.  Strong  sulphuric  acid  dissolves  it  with  dark  brown 
colour ;  the  addition  of  water  precipitates  it  from  this  solution  un- 
changed. Strong  nitric  acid  acts  on  it  with  great  energy,  liberating 
nitrogen  tetroxide  in  profusion,  yielding  a  deep  yellow  solution, 
and  an  insoluble  yellow  acid,  probably  a  nitro  acid.  This  new  acid 
is  soluble  in  alkalies,  from  which  acids  again  precipitate  it.  The 
yellow  nitric  solution  was  not  examined.  The  writer  designates 
this  second  acid  as  "  persiretin."  Tlie  powder  was  found  to  contain 
4"3  per  cent,  of  it.  It  is  not  the  active  principle,  but  a  decom.posi- 
tion  product  of  it. 


MATERIA   MEDICA.  183 

A  third  and  very  soluble  acid  was  found.  This  body  the  writer 
names  "persicin."  It  is  a  glucoside,  and  is  split  by  boiling  with 
acids  into  persiretin  and  glucose.  It  appears  to  be  a  polybasic 
acid,  forming  an  insoluble  and  a  soluble  lead  salt.  It  is  remarkable 
for  having  a  pleasant  odoar  resembling  that  of  fresh  honey.  This 
acid  is  exceedingly  unstable ;  contact  with  dilute  chlorhydric  acid 
in  the  cold  or  evaporation  of  its  solution,  or  of  its  salts,  converts 
it  into  perseretin  and  glucose.  It  is,  therefore,  almost  impossible 
to  obtain  the  free  acid  dry  in  a  pure  state.  The  colour  of  persicin 
is,  in  solution,  light  wine  red,  and  that  of  its  neutral  salts  dark 
wine  red. 

Plumbic  acetate  does  not  precipitate  its  neutral  solutions,  but 
diplumbic  acetate  produces  a  voluminous  greenish  white  precipitate. 
Excess  of  persicin  dissolves  the  neutral  lead  salt,  forming  a  pale 
yellow  solution,  which  on  evaporation  yields  an  amorphous  mass  in- 
soluble in  alcohol,  which  latter  also  precipitates  the  salt  from  its 
aqneous  solution  in  yellowish  white  curdy  flakes. 

The  acid  potassium  salt  of  persicin  can  be  crystallized ;  it  is  also 
soluble  in  alcohol.  The  neutral  salt  is  apparently  amorphous,  and 
but  sparingly  soluble  in  alcohol.  Persicin  gives  a  fresh  coloured 
precipitate  with  argentic  nitrate,  which  is  insoluble  in  acetic  acid, 
but  soluble  in  ammonia.  Persicin  is  soluble  in  alcohol,  but  insoluble 
in  chloroform,  ether,  and  benzine.  It  is  apparently  the  active  prin- 
ciple of  the  plant.  The  investigation  was  conducted  by  percolating 
the  powder  first  with  water  containing  ammonia.  The  aqueous 
percolate  yielded  nothing  to  chloroform.  Addition  of  chlorhydric 
acid  threw  down  the  persiretin.  After  filtration,  ammonia  gave  a 
crystalline  precipitate  of  ammonio-magnesian  phosphate. 

The  ammoniacal  percolate  had  a  ruby  red  colour.  Addition  of 
chlorhydric  acid  precipitated  persiretin  in  great  abundance,  showing 
that  the  small  amount  extracted  by  water  in  the  first  percolation 
existed  in  combination  with  some  base,  but  that  the  most  of  it  is 
uncombined. 

The  acid  filtrate  was  then  ti'eated  with  ammonia  in  excess,  united 
with  the  first  filtrate,  and  the  whole  evaporated  on  a  water  bath  to 
a  syrupy  liquid.  This  residue,  now  having  an  acid  reaction,  was 
treated  with  alcohol,  which  produced  a  gummy  precipitate  and  a 
dark  red  liquid.  The  solution  was  evaporated  on  a  water  bath  to 
expel  alcohol,  slightly  diluted  with  water,  and  shaken  with  ether. 
The  ethereal  solution,  on  spontaneous  evaporation,  yielded  a  I'esidue 
of  persicin.  The  aqueous  residue  was  now  shaken  with  chloroform, 
which  after   decantation   and   evaporation  left   no   residue.      The 


184  TEAE-BOOK   OP   PHARMACY. 

aqueous  liquid  was  then  treated  with  benzine,  which  took  up  the 
ether  and  chloroform  held  in  solution;  on  evaporation  no  appreciable 
residue  was  left,  thus  showing  the  probable  absence  of  alkaloids. 

The  liquid  fx'om  which  the  benzine  had  been  decanted  was  treated 
with  chlorhydric  acid,  producing  a  slight  turbidness  ;  shaken  with 
ether,  it  dissolved,  and  the  yellowish  ethereal  solution  yielded  on 
evaporation  more  of  the  persicin.  This  result  shows  that  the  per- 
sicein  taken  up  by  the  ether  in  the  first  instance  had  parted  with  the 
ammonia  during  the  evaporation,  and  that  the  remainder  could  only 
be  removed  after  its  liberation  by  the  chlorhydric  acid. 

The  red  acid  liquid  was  now  mixed  with  the  filtered  solution  of 
the  matter  precipitated  by  the  alcohol,  neutralized  with  ammonia, 
and  treated  with  diplumbic  acetate  as  long  as  a  precipitate  formed ; 
this  was  collected,  washed,  and  treated  with  dilute  sulphuric  acid  in 
slight  excess,  whereby  the  persicin  was  liberated,  and  the  peculiar 
honey  odour  at  once  became  perceptible.  On  evaporation  on  a 
water  bath,  a  red  acid  residue  was  obtained ;  however,  it  was  much 
contaminated  with  insoluble  persiretin,  into  which  a  part  of  the 
persicin  had  been  converted.  The  fresh  solution  of  the  persicin, 
neutralized  with  potassium  hydrate  and  boiled  with  Pehling's  solu- 
tions, yields  an  emerald  green  liquid,  but  no  cuprous  oxide.  If  the 
solution  is,  however,  first  boiled  a  few  moments  with  dilute  chlor- 
hydric acid  until  it  becomes  turbid,  then  neutralized  and  boiled  with 
Fehling's  solutions,  cuprous  oxide  is  profusely  precipitated.  This 
makes  it  evident  that  persicin  is  a  glucoside,  decomposable  into  per- 
siretin and  glucose. 

XantMum  Spinosum.  M.  Guichard.  (Bepert.  de  Phann.  [N.S.], 
iv.,  513  ;  Pharm.  Journ.,  3rd  series,  vii.,  249.)  The  author  presents 
the  following  contribution  to  the  chemical  and  pharmaceutical  his- 
tory of  this  new  medicament  which  has  recently  been  recommended 
as  a  remedy  for  hydrophobia. 

The  drug  is  met  with  in  the  form  of  stalks  bearing  leaves  and 
numerous  spines.  There  is  room,  therefore,  for  the  study  of  the 
picked  and  unpicked  drug,  and  to  ascertain  which  of  the  two 
should  be  employed,  as  probably  the  activity  of  all  the  parts  is  not 
the  same.  Their  yield  in  extract  is  very  different, — 20  grams  of 
cleaned  leaves  gave  with  alcohol  5  grams,  or  25  per  cent.,  of  green 
extract  containing  much  chlorophyll.  150  grams  of  the  uncleaned 
drug  treated  in  the  same  way  yielded  also  a  green  extract,  but  in 
less  quantity,  the  yield  being  only  12  grams,  or  7|  per  cent.  The 
difierence  was  due  to  chlorophyll. 

The  two  extracts  were  prepared  by  coarsely  powdering  the  plant, 


MATERIA    MEDICA.  185 

and  treating  it  after  twelve  hours'  maceration  by  displacement,  first 
with  90  per  cent.,  and  then  with  60  per  cent,  alcohol. 

128  grams  of  the  unpicked  plant  were  treated  by  infusion,  then 
pressed,  and  treated  a  second  time.  The  product  was  evaporated  on 
a  water  bath,  and  gave  60  grams,  or  39  per  cent.,  of  extract. 

The  alcoholic  extracts  were  very  bitter ;  the  aqueous  extract 
scarcely  so.  The  author  therefore  thinks  that  probably  the  alcoholic 
extract  is  the  most  active,  and  this  appears  to  be  borne  out  by  the 
following  pi-eliminary  experiments  : — 

The  alcoholic  extract  redissolved  in  water  was  precipitated  by 
iodized  iodide  of  potassium,  but  not  by  cadmi-potassic  iodide.  The 
alkalies  precipitated  iron  and  alumina.  When  dried  with  calcined 
magnesia  and  treated  with  ether,  an  extract  was  obtained  which,  if 
redissolved  in  water  acidulated  with  a  few  drops  of  hydrochloric  acid, 
gave  with  the  iodized  iodide  an  abundant  kermes  coloured  precipi- 
tate, and  with  cadmi-potassic  iodide  a  dirty  grey  precipitate  that 
separated  rapidly  like  curdled  milk.  Ammonia  precipitated  the  solu- 
tion slightly. 

If  the  above  aqaeous  solution  be  allowed  to  evaporate  upon  a 
glass  plate  of  a  microscope,  crystals  are  obtained  of  various  forms, 
— such  as  needles  grouped  in  crosses,  or  three-branched  stars,  and 
granular  crystals;  also  some  green  colouring  matter.  The  hydro- 
chloric solution  gives  large  square  or  rectangular  tables,  as  well  as 
acicular  crystals.  The  liquid  precipitated  by  ammonia  contains  a  large 
number  of  amorphous  points  and  numerous  bundles  of  fine  needles. 
The  aqueous  extract  treated  in  the  same  manner  gives  no  results. 
But  the  author  considers  that  the  preceding  experiments  demon- 
strate the  presence  of  an  alkaloid  which  he  hopes  soon  to  be  in  a 
position  to  isolate. 

The  mode  of  employment  of  the  drug  previously  indicated  was  to 
administer  60  centigrams  of  the  plant,  finely  pulverized,  several 
times  a  day. 

Xanthium  Spinosum.  Dr.  Grzymala.  The  author  has  com- 
municated to  the  Journal  cles  Debats  a  most  favourable  report  on  the 
value  of  Xanthium  spinosum  as  a  remedy  for  hydrophobia.  Up- 
wards of  one  hundred  persons  were  cured  by  it  of  this  terrible 
disease.  0'3  gram  of  the  powdered  leaves  is  administered  three 
times  a  day  for  several  weeks.  Of  twelve  hydrophobic  patients  in 
the  hospital  at  Olschanka  (in  the  district  of  Balta),  six  were  com- 
pletely cured  by  the  administration  of  this  herb ;  the  other  six  died 
in  spite  of  the  application  of  cantharides,  faba  tonca,  genista  tinc- 
toria,  etc. 


186 


YEAR-BOOK    OF    PHARMACY. 


The  Mineral  Constituents  of  Xanthium  Spiuosum.  Dr.  R. 
Godeffroy.  {Zeitschr.  des  oesterr  Apoth.  Ver.,  1877,  'ol .)  The 
statement  occurring  in  the  Pharmaceut.  Zeitschrift  fiir  Eussland, 
1876,  4U3,  that  the  ash  of  Xanthium  spinosum  contained  nitrates  is 
contradicted  by  the  author,  who  found  in  100  parts  of  the  ash, — 


Calcium  Carbonate 

9-39 

„      Sulphate 

2-8-4 

„      Phosphate  (CasPO^) 

13-18 

Magnaeium  Carbonate 

8-31 

Chloride   . 

1-07 

Potassium  Carbonate  . 

25  00 

,,          Chloride 

4-39 

Sodium  Carbonate 

traces 

Silica 

19-73 

Ferric  Oxide 

15-81 

Aluminium  Oxide 

traces 

Fncus  Vesiculosus,  and  Allied  Species.  J.  M.  Maisch.  (Amer. 
Journ.  Pharm.,  September,  1876.)  Though  Theophrastus  already, 
in  his  history  of  plants,  mentions  several  species  of  marine  algee,  the 
sea  -wrack  does  not  appear  to  have  been  employed  medicinally  be- 
fore the  first  half  of  the  eighteenth  century ;  at  least  no  mention  is 
made  of  it  in  the  new  "  London  Dispensatory  "  of  1676.  Russell 
seems  to  have  been  instrumental  in  introducing  it  into  medicine 
through  his  essay,  "  De  talie  glandularis'"  which  was  published  in 
1750,  and  in  which  he  specially  recommended  Fncus  vesiculosus  in 
the  form  of  charcoal  and  jelly  ;  the  former,  known  afterwards  under 
the  name  of  JEthiops  vegetabilis,  being  prepared  by  heating  the 
plant  in  a  crucible  closed  with  a  perforated  cover  until  smoke  ceased 
to  be  given  off,  while  the  latter  was  made  by  expressing  the  muci- 
laginous liquid,  and  also  by  macerating  the  fucus  in  an  equal  weight 
of  sea  water  for  two  weeks,  or  until  it  was  converted  into  a  kind  of 
jelly,  which  was  employed  both  externally  and  internally.  Upon 
the  strength  of  these  observations,  Fucus  vesiculosiis  was  admitted 
into  several  pharmacopoeias,  but  was  afterwards  dismissed,  the  last 
one  dropping  it  being  the  Dublin  Pharmacopoeia,  in  the  edition  of 
1850.  The  beneficial  effects  in  scrofulous  swellings  and  goitre  of 
the  vegetable  ethiops  and  of  the  sponge  charcoal,  which  had  been 
introduced  by  Arnaud  de  Villeneuve  near  the  close  of  the  thirteenth 
century,  and  the  discovery  of  iodine  in  the  ashes  of  sea  plants, 
induced  Dr.  Coindet,  of  Geneva,  in  1819,  to  study  the  effects  of 
iodine,  and  led  to  the  introduction  of  this  element  into  medicine. 
Subsequently,  Duchesne   Dupare,  and  after  him  Godsfrey,  stated 


MA'IEniA    MEDICA.  187 

(1862)  that  they  had  found  this  fucus  to  possess  valuable  properties 
as  a  remedy  for  morbid  obesity,  an  observation  which,  by  later 
investigators,  does  not  appear  to  be  confirmed  to  the  fall  extent 
mentioned  by  the  first  recommenders  in  this  complaint. 

Of  late,  the  bladder  wrack,  it  seems,  has  been  employed  medici- 
nally to  some  extent  in  the  United  States;  so  that  a  brief  description 
of  this  and  some  allied  species  may  be  desirable. 

The  genus  Fucus  belongs  to  the  sub-order  Fucoidece,  or  melano- 
sporea3,  of  the  natural  order  Algce.  As  originally  constituted  by 
Linnceus,  it  embraced  several  genera  which  have  been  separated 
by  later  authors,  and  among  which  are  the  genera  Laminaria, 
Sargassum,  and  Ci/stoseira,  the  last  named  having  the  thallus  usually 
inflated  into  vesicles  which  often  show  a  moniliform  arrangement, 
while  the  vesicles  of  8argassum  are  stipitate.  Fucuf:  has  either  a 
cylindrical  (filiform)  or  flat,  usually  forking  thallus,  and  the  sporo- 
carps  inflated  and  usually  terminating  the  branches.  In  their  fresh 
state  they  have  an  olive  or  brownish  green  colour,  becoming  black- 
ish on  drying.  Several  species  have  portions  of  the  thallus  inflated 
so  as  to  form  hollow  vesicles. 

Fucus  vesiculosus,  Lin.,  attains  the  length  of  one  to  three  feet,  and 
has  a  flat  thallus  one-half  to  one  inch  wide,  with  the  margin  entire, 
and  a  distinct  midrib  running  the  entire  length  of  the  thallus  ;  the 
vesicles  are  always  in  pairs,  one  being  placed  on  each  side  of  the 
midrib,  spherical  or  oblong  globular  in  shape,  and  occasionally 
attaining  the  size  of  a  hazel  nut.  It  grows  on  rocky  sea-shores  of 
the  Atlantic  Ocean,  near  high  water  mark,  and  in  marshes  which 
are  occasionally  overflowed  by  the  tide.  Formerly  it  was  known  by 
the  name  of  Quercus  marina,  or  sea  oak,  its  common  English  names 
being  bladder  wrack,  sea  wrack,  sea  ware,  kelp  ware,  and  black 
tang.  In  Scotland  and  other  northern  countries  it  is  used  in  winter 
for  feeding  horses,  cattle  and  sheep,  and  is  eaten  by  deer  when 
other  food  is  scarce. 

F.  nodosus,  Lin.,  knobbed  sea  wrack,  grows  in  similar  localities, 
but  at  or  near  low  water  mark.  It  attains  a  length  of  four  to  six 
feet,  and  has  a  narrower  veinless  frond,  with  the  branches  almost 
filiform  at  the  base,  the  vesicles  single  in  the  centre  of  the  thallus, 
or  frond,  ovate  in  shape,  and  usually  quite  large. 

F.  serrafus,  Lin.,  has  a  veined  and  serrate  frond,  and  is  destitute 
of  vesicles. 

F.  slUquosus,  Lin.  (s.  Ci/stoseira  siliquosa,  Agardh),  has  a  very 
narrow  frond,  two  to  four  feet  long,  with  short  branches,  articulated 
vesicles,  and  lanceolate  flattened  sporocarps. 


188  TEAR-BOOK    OF    PHARMACY. 

F.  natans,  Lin.  (s.  Sargassum  bacciferum,  Agardh),  the  gulf-weed 
of  the  Atlantic  Ocean,  is  often  found  in  immense  masses  floating  in 
the  sea.  Its  frond  is  terete,  with  the  branches  linear  and  serrate, 
and  the  vesicles  globular  and  aculeate. 

All  these  and  many  allied  species  appear  to  be  very  similar  in 
their  constituents,  of  which  they  contain  mucilage,  mannite,  odorous 
oil,  bitter  principle,  and  a  considerable  proportion  of  saline  matter, 
varying  from  14  to  20  per  cent.,  calculated  for  the  dry  plants. 
According  to  Godeschen,  James,  and  others,  the  variation  is  just  as 
great  for  the  bladder  wrack  as  collected  in  different  localities,  and 
it  is  not  impossible  that  this  may  be,  at  least  in  part,  accounted  for 
by  having  been  collected  in  different  seasons,  the  plant  being  as- 
sumed to  be  most  active  when  collected  after  the  sporocarps  have 
formed,  about  the  month  of  July.  E.  Marchand  found  (1865)  in 
the  ashes  of  F.  vesiculosus  0  719  per  cent,  iodine  and  0'603  per  cent, 
bromine  ;  in  F.  siliquosus  nearly  the  same  amount,  and  in  F.  serrntus 
0834  iodine  and  1'007  bromine;  while  the  ashes  of  the  fucoideoe, 
Laminaria  agitata,  Lamx.,  contained  5'3o2  iodine  and  0" 7 74  bromine, 
and  Lam.  saccharina,  Lamx.,  about  one-half  these  amounts.  (See 
also  American  Journal  of  Pharmacy ,  1854,  p.  438.) 

Bladder  wrack  has  been  employed  in  France  in  the  form  of 
extract,  prepared,  according  to  Dannecy,  by  exhausting  the  plant 
with  54  per  cent,  alcohol ;  it  is  stated  to  represent  fifteen  parts  of 
the  fucus  {Proc.  Am.,  Phar.  Assoc,  1863,  p.  66)  ;  also  in  the  form  of 
syrup,  suggested  by  Potier  {Ibifl.),  by  exhausting  150  parts  of  the 
powdered  plant  with  14  per  cent,  alcohol,  evaporating  the  tincture 
to  230  parts,  and  dissolving  in  it  370  parts  of  sugar.  20  grams  (one 
tablespoonful)  of  this  syrup  represents  0'6  gram  of  the  extract  and 
5  grams  of  the  fucus,  which  is  the  average  dose.  A  fluid  extract 
might  doubtless  be  prepared  by  a  process  similar  to  the  ofiicinal  one 
for  fluid  extract  of  chimaphila ;  the  average  dose  of  such  a  prepara- 
tion would  be  about  a  teaspoonful.  If,  however,  the  virtues  depend 
mainly  upon  the  iodine  and  bromine  present,  the  dose  would  have 
to  be  increased  very  considei-ably. 

A  New  Alkaloid  in  Angostura  Bark.  MM.  Oberlin  and 
Schlagdenhauffen.  (Bepert.  de  Pharm.,  1877,  No.  9.)  The 
authors  have  isolated  from  the  bark  of  Galipea  Cusparia  a  crystal- 
lizable  alkaloid  which  is  soluble  in  ether,  chloroform,  and  benzoline, 
and  entirely  different  from  Saladin's  cusparine.  They  have  adopted 
the  same  name  (cusparine)  for  their  own  alkaloid. 

Note  on  Sumbul.  K.  Wittmann.  (Pharm.  Journ.,  from  Pkar- 
maceut.  Zeltschr.  fdr  Russland.)     After  referi'ing  to  a  notice  which 


MATERIA    MEDICA.  189 

appeared  last  year  in  the  Pharmaceutial  Journal  (vol.  vi.,  p.  43), 
respecting  the  blooming  of  the  sumbal  plant  at  Kew,  the  author, 
who  is  Secretary  to  the  Military  Medical  District  Administration  of 
East  Siberia,  gives  the  following  information  : — 

The  Eurijangium  sumhul  is  found  in  large  quantities  in  the 
neighbourhood  of  Chabarowka,  a  military  post  on  the  river  Amur, 
in  the  province  of  Kiisten,  East  Siberia,  9000  versts  from  St. 
Petersburg!!.  It  is  a  perennial  umbellifer,  and  grows  to  the  height 
of  from  three  to  five  feet.  Its  root  is  branched,  fleshy,  about  eleven 
inches  in  circumference  at  the  base,  and  three  and  three-quarter 
inches  in  diameter,  with  numerous  rootlets,  and  covered  with  a 
brown  bark.  The  root  has  a  strong  smell  of  musk,  which  by 
moistening  with  water  is  considerably  increased.  The  stalk  of  the 
plant  is  always  fleshy,  equal  in  circumference  at  the  base  with  the 
x'oot,  becoming  gradually  more  slender  towards  the  top.  The  leaves 
are  more  than  twice  pinnatifid ;  the  pinnge  lancet-shaped,  sharply 
serrate ;  the  umbels  with  thirty  to  fifty  rays ;  the  flowers  white  and 
small. 

Besides  the  Euryangium  sumhul,  the  author  has  met  with  an- 
other umbellifer  which  resembles  it  vei'y  much  in  its  entire  habit, 
but  may  be  distinguished  by  its  smaller  size,  lighter  leaves,  and  the 
absence  of  the  musk-like  smell  of  the  root. 

The  Eastern  Russian  inhabitants  call  the  Eiiryangmm  sumhul 
"bararklane  "  (bear's  claw),  and  use  the  root  as  a  medicine.  The 
Chinese  living  in  the  district  use  the  root  of  the  plant  against 
various  diseases,  and  call  it  "  Isoumal-tschen-tuk."  It  is  also  used 
by  the  natives  internally  as  a  remedy  for  swellings ;  with  them  it 
bears  the  names  "  ofuokgi  "  and  "  ouchi."  The  author  promises  a 
future  communication,  giving  the  results  of  an  examination  of  the 
separate  constituents  of  the  root  as  it  is  found  in  the  district  of 
Chabarowka. 

Ailanthus  Glandulosa  in  Dysentery.  Dr.  J.  Dudgeon.  {Med. 
Times  and  Gazette,  October  28th,  1876.)  The  Ailanthus  is  a  very 
common  tree  in  north  China,  growing  readily  and  rapidly,  and 
attaining  a  considerable  height.  The  Chinese  note  two  varieties, 
the  fragrant  and  the  fetid.  Two  synonyms  for  the  latter  tree  are 
given — "  tiger's  eye,"  from  the  resemblance  of  the  facets,  when  the 
branches  fall  off  from  the  main  stem,  to  that  animal's  eye;  and 
"  great  eye  varnish,"  from  which  circumstance  the  French  name 
"  vernis  du  japon "  may  be  derived.  The  Chinese  name  has  no 
connection  with  the  word  ailanto,  which  is  supposed  in  Europe  to 
be  its  native  name  in  China  and  India,  and  is  thought  to  mean 


190  YEAR-BOOK    OF    PHARMACr. 

"tree  of  tbo  gods."  It  is  intensely  bitter  and  astringent,  of  a 
Avarm  taste,  free  from  poison,  and  emits  a  disagreeable  smell,  from 
which  latter  circumstances  its  Chinese  name  is  derived.  The 
Chinese  medical  works  recommend  it  as  an  antidote  against 
sulphur,  arsenic,  and  gold  poisoning.  It  is  said,  also,  to  possess 
anthelmintic  properties,  and  to  be  used  in  demonology  against 
the  supposed  transfer  of  disease  from  a  corpse.  It  is  also  useful 
in  diarrhoea,  prolapsus  aui,  and  leucorrhoea.  It  is  frequently  pre- 
scribed alone ;  at  other  times  in  conjunction  with  other  remedies, 
particularly  Eadix  hedysari  and  the  fruit  of  TerminaUa  chehula, — 
favourite  remedies  in  diarrhoea  and  dysentery, — which  increase  its 
efficacy.  It  is  strongly  recommended  in  all  cases  of  htemorrhage, 
from  whatever  cause  or  locality.  It  is  used,  too,  in  gonorrhoea  and 
spermatorrhoea,  and  in  short,  in  fluxes  in  general.  The  part  used  is 
the  inner  white  bark  of  the  root  and  stem  of  the  non-fragrant 
species.  Whether  taken  in  infusion  or  in  a  pill,  it  is  invariably 
prescribed  to  be  taken  on  an  empty  stomach,  in  congee  or  with  milk 
or  soft  boiled  rice.  In  the  most  severe  cases  it  is  taken  in  conjunc- 
tion with  Castus  amainis  and  vinegar. 

Pumpkin  Seeds  and  their  Active  Principle.  (From  Phann. 
Zeitunrj,  1877,  No.  55.)  The  nature  and  location  of  the  active 
principle  of  the  pumpkin  seeds  appears  to  have  been  determined  by 
Heckel,  of  Nancy,  who  has  published  an  interesting  memoir  on  this 
subject.  In  the  French  drug  trade  pumpkin  seeds  are  derived  from 
Gucurbita  viaxima,  C.  Tepo,  and  C.  moschata,  which  are  equally 
serviceable  against  tape- worm,  while  the  black  seeds  of  G.  vielano- 
carpa,  or  the  seeds  of  the  closely  related  genus  Giicuviis,  are  entirely 
devoid  of  medicinal  value,  since  the  tAvo  latter  lack  the  very  mem- 
brane in  which  the  active  principle  resides.  The  seeds  of  the  thi-ee 
first-mentioned  species  differ  chiefly  in  dimensions  and  colour.  Those 
of  C.  Pepo  (pumpkin)  are  the  smallest,  having  an  average  length  of 
6-7  millimetres,  rarely  as  much  as  20-25  mm.;  they  are  oblong- 
ovate,  have  a  groove  along  both  edges,  where  they  are  thickened, 
and  have  a  dirty  white  colour.  The  seeds  of  C.  maxima  are  18-25 
mm.  long,  by  10-15  mm.  broad,  are  regularly  oval,  and  vary  in 
colour  from  white  to  orange.  G.  moschata  has  slightly  smaller  seeds, 
16-22  mm.  long  and  9-12  mm.  broad,  pure  white,  grooved,  and  the 
surrounding  thickened  edge  of  darker  colour.  These  three  varieties 
of  seeds  consist  of  a  perisperm  made  up  of  four  coats,  and  an  embryo 
with  two  thick  oily  cotyledons.  The  most  external  coat  of  the 
perisperm  is  an  exceedingly  fine  membrane,  constructed  from  a  single 
layer  of  oblong  cells,  which  imparts  to  certain  varieties  a  character- 


MATERIA    MEDICA.  191 

istic  silver-grey  appearance.  Below  this  lies  the  tougher  testa,  made 
up  from  singularly  polyedric,  finely  incrusted  cells  filled  with  starch. 
Both  of  these  coats  are  removed  by  washing  the  dried  seeds,  while 
the  washing  o^ fresh  seeds  removes  also  the  next  two  coats.  The 
first  of  these — the  third  coat,  counting  from  outside — is  dirty-white, 
of  a  loose  and  spongy  texture,  and  consists  of  spherical  reticulated 
cells.  The  fourth  and  innermost  coat,  finally,  which  has  a  dark 
green  colour  when  fresh,  changing  gradually  to  greenish  yellow, 
has  a  chartaceous  appearance  and  consists  of  two  layers  :  the  outer 
one  made  up  of  hexagonal  or  pentagonal  cells  with  moderately  thick 
walls,  including  chlorophyll  and  a  resinous  mass;  the  inner  one 
formed  by  elongated  cells,  including  starch.  The  resinous  mass  in 
the  outer  layer  of  the  fourth  or  innermost  coat  of  the  seeds  is,  ac- 
cording to  Heckel,  the  active  tsenicidal  principle,  and  not,  as  has 
been  supposed,  the  fatty  oil  residing  in  the  cotyledons.  Owino-  to 
the  absence  of  this  papyraceous  membrane,  which  alone  contains 
the  resin,  in  other  cucurbitaceous  seeds,  these  latter  are  inert.  At 
the  same  time  it  is  shown  that  even  active  seeds  become  inert,  when 
they  are  blanched  in  a  fresh ^  state,  as  all  the  coats  are  thereby 
removed. 

Mate,  or  Paraguayan  Tea.  Dr.  Bialet.  (Abstract  of  a  report 
in  the  Mevista  Farmaceutica;  Pharm.  Jown.,  3rd  series,  vii.,  4.)  The 
mate,  or  Paraguay  tea  tree  (Ilex  mate  paraguayensis)  is  a  small  tree 
belonging  to  the  family  of  Celastrinece,  which  reaches  at  tlie  most 
a  height  of  seven  metres ;  ordinarily  it  does  not  exceed  four  or 
five.  Its  trunk  is  about  twenty  centimetres  in  circumference,  and 
is  covered  by  a  whitish  bark.  The  leaves  are  oblong,  cuneiform, 
obtuse,  and  finely  dentate.  It  has  axillary  multipartite  peduncles  ; 
calyx  tetrasepalous  ;  the  corolla  with  four  petals  in  the  form  of  a 
crown;  stile,  none;  stigma,  four-fid;  fruit,  a  four-seeded  berry.  The 
plant  grows  very  abundantly  in  Paraguay,  North  Corrientes,  Chaco, 
and  South  Brazil,  where  it  forms  woods  called  "^er&aZes." 

According  to  Dr.  Mantegazza,  mate  is  prepared  in  Paraguay  in 
the  following  way : — The  entire  trees  are  cut  down,  and  the  small 
branches  and  shoots  are  taken  with  the  leaves  and  placed  in  the 
tataciia,  a  plot  of  earth  about  six  feet  square  surrounded  by  a 
fire,  where  the  plant  undergoes  the  first  roasting.  From  thence 
it  is  taken  to  the  barbaciia,  which  is  a  grating  supported  by  a 
strong  arch,  underneath  which  burns  a  large  fire  ;  here  it  is  sub- 
mitted to  a  particular  torrefaction,  determined  by  experience,  which 
develops  the  aromatic  pi'inciple.  Then  it  is  reduced  to  a  coarse 
powder  in  mortars  formed  of  pits  dug  in  the  earth  and  well  rammed. 


192 


YEAR-BOOK    OF   PHARMACY. 


It  is  next  put  into  fresh  bullock  skins,  well  pressed,  and  placed  in  the 
sun  to  dry.  The  packages  (tercois)  thus  obtained,  which  weigh  90 
to  100  kilograms,  are  very  compact ;  and  have  an  average  value  in 
commerce  of  one  to  two  dollars  the  kilo.,  according  to  quality;  those 
of  Paraguay  and  Missiones  being  the  better,  or  least  hurtful,  those 
of  Oi'an  and  Paranagua  being  much  more  prejudicial  to  health. 

Of  all  the  analyses  of  mate  that  have  appeared  in  books.  Dr.  Bialet 
considers  not  one,  up  to  the  present  time,  deserves  much  credit. 
Senor  Arata,  however,  who  has  devoted  much  time  and  skill  to  the 
subject,  has  placed  the  following  data  at  his  service  : — 

Mate  contains  in  100  parts  : — 


Organic  combustible  substances 
Ash 


The  ash  contains : — 


Calcium  Oxide 

Magnesium  Oxide 

Sodiiim  Oxide 

Potassium  Oxide  . 

Manganese  Oxide 

Ferric  Oxide 

Sulphuric  Acid 

Hydi'ochloric  Acid 

Phosphoric  Acid   . 

Carbonic  Acid 

Sand,  Silica,  Carbon,  and  loss 


91-685 
8-315 


12-344 
11-395 
7-281 
2-984 
2-500 
3-410 
0-926 
0-716 
5-540 
8-150 
44-754 


It  will  be  understood  that  the  enormous   relative   quantities   of 

sand  found  in  the  analysis  is  a  result  of  the  mode  of  preparation  in 
excavations  made  in  the  soil. 

The  plant  contains : — 

Principles  soluble  in  Ether  ....  9-820 

Alcohol          .         .         .  8-432 

Water   ....  26-208 
,,                ,,        Water    acidulated  with 

Hydrochloric  Acid 7-260 

In  solution  of  Caustic  Soda  ....  16-880 

Cellulose 13-280 

Water 9000 

Sand     .                 9-120 


100-000 


'  Among  the  soluble  principles  is  an  average  of  1'300  of  caffeine. 
The  quantity,  however,  was  found  to  be  very  variable  in  different 
plants  analysed ;  the  Paraguay  and  Missiones  contained  the  most, 


IIATERIA   MEDICA.  193 

and  the  Paranagua  and  Argentine  the  least.  Senor  Arata  has  made 
a  careful  search  for  caffeic  acid,  and  the  cafFeates  that  some  say  they 
have  found  in  mate,  but  hitherto  always  with  negative  results ;  the 
same  remark  applies  to  the  examination  for  a  volatile  acid. 

The  tannin  of  mate  is  peculiar ;  it  does  not  tan  hides,  and  requires 
a  special  method  for  its  estimation.  The  average  amount  obtained 
by  the  ordinary  method  is  not  more  than  12  per  cent. ;  but  the 
whole  quantity  present  amounts  to  about  16  per  cent. 

Mate  contains  also  a  large  quantity  of  a  peculiar  fatty  matter,  not 
entirely  saponifiable  by  potash,  besides  pectic  matters. 

Comparing  mate  with  the  other  cafFeic  substances,  it  ranks 
between  coffee  and  tea  for  the  proportion  of  caffeine  it  contains,  and 
has  the  largest  proportion  of  mineral  salts. 

The  action  of  mate,  like  that  of  all  other  caffeic  substances,  is 
upon  the  nervous  system,  but  though  it  contains  a  large  quantity  of 
caffeine  it  does  not  exalt  the  peripheric  nerves  like  tea,  nor  the 
cerebric  like  coffee ;  but  rather  contributes  in  a  high  degree  to  the 
indolence  and  drowsiness  of  the  ordinary  drinkers  of  mate,  whose 
mental  faculties  become  at  length  disarranged  and  impoverished  to 
a  lamentable  degree.  It  accelerates  the  cardiac  conti-actions,  produc- 
ing many  more  affections  of  the  heart  than  tea  or  coffee.  Upon  the 
digestive  organs,  it  acts  variously;  no  other  beverage  disturbs  them 
so  much,  though  there  are  persons  who  can  tolerate  its  use.  It  ac- 
celerates the  peristaltic  movements,  and  produces  an  irritation  of  the 
organs  generally.  These  effects  are  produced  in  whatever  way  the 
mate  may  be  taken;  but  the  most  injurious  effects  are  produced 
upon  the  mucous  membrane,  when  the  mate  is  taken  hot  and  is 
sucked  through  a  "  bombilla,"  as  it  then  passes  into  the  stomach 
uncooled  by  previous  contact  with  the  mouth. 

"When  the  use  of  mate  is  prolonged,  it  becomes  an  impei'ious 
necessity,  such  a  gloominess  following  abstention  from  it,  that 
habitual  drinkers  would  rather  go  without  food  than  without  mate. 
The  moderate  use  of  two  or  three  doses  a  day  dui'ing  the  summer 
heats  or  great  fatigue  is  convenient,  but  it  should  be  taken  from 
a  cup.  It  adds  to  the  disadvantage  of  the  "  bombilla,"  that  by 
indiscriminate  use  of  the  same  bombilla  by  different  persons,  it 
may  become  the  vehicle  of  contagion  for  the  most  repulsive  com- 
plaints. 

The  Seeds  of  Eicinus  Communis.  E.  L.  Boerner.  (From  an  in- 
augural essay:  Amer.  Journ.  Phartn.,  Nov.,  1876.)  The  acrid  princi- 
ple of  ricinus  seeds  is  but  in  a  slight  degree  extracted  in  the 
expression  of  the  oil ;  and  the  residual  marc,  as  left  by  the  manu- 

0 


194  TEAR-BOOK   OF   PHARMACY. 

facttirer  of  castor  oil,  -svould,  therefore,  contain  the  greater  portion 
of  it,  and  was  the  material  operated  upon. 

The  coarse  particles  which  were  liable  to  interfere  with  perco- 
lation being  rejected,  four  different  portions,  of  1000  grains  each, 
were  treated  respectively  with  gasolin,  bisulphide  of  carbon,  ether, 
and  alcohol,  until  exhausted ;  the  various  menstrua  evaporated,  and 
the  residues  weighed,  yielding  from  gasolin,  6'9  per  cent. ;  bisul- 
phide of  carbon,  11-77  per  cent.  ;  ether,  14  per  cent. ;  and  alcohol, 
21"2  per  cent.  The  first  three  appeared  to  be  pure  oil,  and  were  of 
a  light  yellow  colour,  while  the  alcohol  residue  was  much  darker, 
and  contained  considerable  colouring  matter,  which  was  deposited 
upon  standing. 

The  marc  which  had  been  exhausted  with  gasolin  was  further 
treated  with  bisulphide  of  carbon,  resulting  in  an  additional  6-o7 
per  cent,  of  oily  residue,  from  which,  after  a  few  days'  standing, 
acicular  crystals  separated,  which  were  insoluble  in  gasolin,  partly 
soluble  in  ether  and  in  alcohol.  A  second  attempt  to  obtain  the 
crystals  was  unsuccessful.  That  portion  of  marc  which  had  been 
treated  with  bisulphide  of  carbon  yielded  nothing  to  gasolin  upon 
subsequent  treatment  with  this  menstruum. 

A  portion  of  exhausted  marc  was  macerated  with  water  until 
decomposed,  requiring  for  the  process  about  fourteen  days.  It  was 
then  strained,  to,  separate  coarser  particles,  and  distilled ;  the  dis- 
tillate, having  an  acid  reaction  and  an  odour  resembling  that  of 
decayed  cheese,  was  treated  with  carbonate  of  zinc,  and  filtered ; 
upon  concentration  of  the  filtrate,  crystals  of  butyrate  of  zinc  sepa- 
rated. Both  crystals  and  mother-liquor,  when  shaken  with  sulphuric 
acid  and  alcohol,  immediately  developed  in  a  marked  degree  the 
odour  of  butyric  ether.  A  portion  of  this  ethereal  liquid,  neutralized 
with  ammonia,  was  unaffected  by  the  addition  of  ferric  chloride,  thus 
indicating  the  absence  of  an  acetate. 

An  experiment  was  made  similar  to  the  one  of  Professor  Tuson,  in 
which  he  found  a  crystallizable  substance  supposed  to  be  an  alkaloid. 

A  portion  of  the  marc  was  boiled  with  successive  portions  of 
water,  the  several  liquids  strained  through  muslin,  and  the  result- 
ing decoction  evaporated  to  the  consistence  of  a  soft  extract,  which 
was  exhausted  with  boiling  alcohol.  Upon  standing,  a  substance 
of  a  resinous  appearance,"  but  soluble  in  water,  separated  from  the 
filtrate,  and  was  removed  by  a  second  filtration.  The  filtrate  was 
concentrated,  and,  as  no  crystals  separated,  magnesia  was  added,  the 
mixture  evaporated  to  dryness,  again  exhausted  with  boiling  alcohol, 
and  filtered,  when,  upon  concentration  and  a  few  days'  stranding. 


IIATKHIA    JtEDICA.  195 

colourless  crystals,  having  the  form  of  rectangular  prisms  and  tables, 
separated,  answering  to  the  appearance  of  those  obtained  by  Pro- 
fessor Tuson.  These  crystals  were  slowly  soluble  in  hot  water.  In 
an  acidulated  solution  of  the  crystals,  phosphomolybdic  acid,  tannic 
acid,  and  iodohydrargyrate  of  potassium  produced  neither  a  pre- 
cipitate nor  a  coloration  ;  while  in  the  mother-liquor  precipitates 
were  at  once  formed  by  the  two  first-named  reagents,  but  by  the 
last  one  only  after  some  houi's,  and  in  amount  about  one-eighth  that 
formed  by  the  phosphomolybdic  acid.  The  mother-liquor,  when 
heated  with  solid  hydrate  of  potassium,  developed  the  odour  of 
ammonia.  From  these  results  the  writer  concludes  that  the  crys- 
talline substance  in  question  is  not  an  alkaloid. 

A  substance  resembling  emulsin  was  obtained  by  forming  an 
emulsion  of  the  marc  with  water,  adding  an  equal  bulk  of  ether, 
and  agitating  repeatedly  for  twenty-four  hours,  when,  upon  stand- 
ing, the  liquid  separated  into  two  layers  ;  the  supernatant  liquid 
being  removed,  alcohol  was  added  to  the  other,  which  precipitated 
the  emulsin.  This  emulsin,  with  amygdalin,  in  the  presence  of 
water,  developed  the  odour  of  hydrocyanic  acid  after  several  days' 
standing.  The  result  of  Mr.  H.  Bower  (American  Journal  of  Phar- 
rnacij,  1854,  p.  208)  is  confii'med  by  this  experiment. 

The  residue  obtained  from  the  alcoholic  percolate  having  deposited 
a  semi-solid  portion  largely  composed  of  colouring  matter,  was 
agitated  with  ether,  which  took  up  the  oil.  The  part  left  undis- 
solved by  the  ether  was  treated  with  successive  portions  of  alcohol 
until  but  a  few  grains  were  left ;  this,  containing  a  number  of 
minute  crystals,  and  having  a  very  sweet  taste,  was  dissolved  in 
water.  The  application  of  Trommer's  test  proved  the  presence  of 
sugar.  A  drop  of  the  aqueous  solution,  placed  on  a  microscope  slide 
and  evaporated,  plainly  revealed  the  presence  of  cane  sugar. 

As  the  best  authorities  agreed  in  placing  the  amount  of  fixed  oil 
obtained  from  the  kernels  of  the  seeds  at  less  than  -jO  per  cent.,  it 
would  seem  that,  as  more  than  11  per  cent,  is  obtainable  from  the 
marc  as  rejected  by  the  manufacturer  by  treatment  with  bisulphide 
of  carbon,  the  latter  oil  could  be  produced  at  a  less  cost  than  an 
inferior  quality  of  the  expressed  article,  and  answer  the  same  pur- 
pose for  use  in  the  arts. 

The  writer  intends  making  further  experiments  to  determine  the 
amount  of  butyric  acid  obtainable  from  the  marc,  by  a  process 
similar  to  the  one  above  described. 

New  Italian  Variety  of  Liquorice  Extract.  A,  Peltz.  (Pharm. 
Journ.,  from  Pharmaceut.  Zeifschr.  fur  E^tssland,  xv.,   257.)     The 


196 


YEAR-BOOK   OF    PHARMACY. 


author  reports  on  a  new  variety  of  liquorice  extract  which  he  had 
received  for  examination  from  a  Russian  wholesale  house.  It  occurs 
in  irregular  masses,  is  rather  tough,  but  can  be  cut  with  a  knife ; 
has  a  dull  appearance,  and  possesses  a  purely  sweet,  uot  burnt, 
taste.  On  dissolving  it  in  water  it  left  but  a  very  small  residue  ; 
and  the  solution,  when  evaporated  on  a  water  bath  yielded  75  per 
cent,  of  extract  dried  at  00°  C.  The  undissolved  residue  was  washed 
with  a  weak  solution  of  ammonia,  then  boiled  with  watei','  and  the 
liquid  tested  with  tincture  of  iodine,  which  gave  a  distinct  indication 
of  starch. 

To  ascertain  the  amount  of  glycyrrhizin  10  grams  of  the  liquorice 
were  dissolved  in  water,  filtered,  the  filtered  solution  mixed  with  a 
sufficient  quantity  of  dilute  sulphuric  acid,  and  the  precipitate  col- 
lected on  a  filter  and  washed.  As  this  did  not  give  the  glycyrrhizin 
sufficiently  pure,  the  precipitate  was  again  dissolved  in  weak  solu- 
tion of  ammonia  and  reprecipitated  with  sulphuric  acid.  This  pre- 
cipitate was  dried,  triturated  with  one-third  of  its  weight  of  barium 
carbonate,  and  extracted  with  hot  absolute  alcohol.  The  alcoholic 
extract  evaporated  to  dryness  gave  1"5  gram  of  glycyrrhizin. 

The  amount  of  sugar  was  ascertained  by  means  of  the  copper 
solution  to  be  10  per  cent. ;  the  loss  in  moisture  when  dried  at 
100°  amounted  to  14  per  cent. 

The  following  table  shows  the  position  of  the  new  substance  in 
relation  to  other  commercial  liquorices  : — 


Variety. 

Moisture 
per  cent. 

Dried 
Extract 
per  cent. 

Glycyr- 
rhizin 
per  cent. 

Starch 
per  cent. 

Sugar 
per  cent. 

English     . 

1-2 

38 

2-44 

27-10 

13 

Calabriau. 

20 

47 

1-33 

35-50 

11 

Bayoune  . 

3-7 

48 

219 

3510 

14 

Astracliau. 

7-3 

50 

18-14 

1-33 

12 

Spanish    . 

4-12 

55 

315 

8-85 

14 

Kasan 

4-5 

57 

14-74 

2-62 

14 

SiciMan    . 

41 

60-5 

4-(37 

5-00 

IG 

Baracco    . 

3-7 

67-5 

4-95 

1312 

15 

Morean     . 

— 

7^-0 

11-88 

5-33 

10 

ItaUau 

140 

750 

15-0 

2-50 

10 

It  will  be  seen  that  though  the  Morean  variety  yields  more  ex- 
tract, it  is  accounted  for  by  the  amount  of  sugar  ;  whilst  the  Kasan 
variety,  which  contains  almost  the  same  amouut  of  glycyrrhizin  as 
the  Italian,  has  the  disadvantage  of  an  unpleasant,  almost  tarry 
taste.  The  new  article,  notwithstanding  its  good  qualities,  is  said 
to  have  been  offered  at  a  low  price. 


MATERIA    MEDICA.  197 

Megarrhiza  Californica,  Torrey.  J.  P.  Heaney.  (Abstract  of  an 
inaiig^ural  essay:  Amer.  Journ.  Pharm.,  October,  1876,  451.)  This 
plant,  better  known  by  the  synonyms  of  the  "  big"  or  "giant  root  " 
and  "manroot,"is  a  herbaceous,  climbing,  and  succulent  vine,  grow- 
ing abundantly  throughout  the  State.  It  is  closely  allied  to  the 
echinocystis  of  the  Eastern  States,  and  also  to  a  new  species  called 
Marah  mvricattts,  or  California  balsam  apple,  which  has  been  de- 
scribed by  Dr.  Kellogg  in  the  proceedings  of  the  California  Academy 
of  Natural  Sciences  (vol.  i.).  It  is  found  both  in  dry,  sandy,  and 
rich  soil.  In  the  former  it  grows  in  bushy  tufts,  about  two  feet  high 
and  four  or  more  wide,  being  evidently  somewhat  stunted  ;  but  in 
rich  soil,  when  well  shaded,  its  annual  stem  climbs  thirty  to  forty 
feet  over  trees,  and  acquires  its  largest  growth.  It  flowers  in 
March  and  April. 

The  most  remarkable  feature  of  this  plant  is  its  gigantic  root, 
which  is  perennial,  tubero-fusiform,  externally  of  a  yellowish  grey 
colour,  and  rugose ;  within  white,  succulent  and  fleshy,  of  a  nause- 
ous odour,  which  is  lost  in  a  great  measure  by  drying,  and  of  a 
bitter,  acrid,  and  disagreeable  taste,  which  leaves  a  feeling  of  acridity 
5n  the  fauces.  The  Indians  are  said  to  use  this  root  as  a  drastic 
■purge  in  dropsy.  It  has  also  been  used  by  domestic  practitioners, 
in  the  form  of  decoction,  both  as  a  laxative  and  cathartic,  with  good 
results.  On  drying,  the  root  lost  from  70  to  75  per  cent,  in  weight. 
The  dried  root  is  externally  of  a  yellowish  brown  colour,  and  longi- 
tudinally wrinkled ;  internally  of  a  white  colour,  becoming  some- 
what darker  by  age,  concentrically  striated,  light,  brittle,  and 
readily  pulverizable,  yielding  a  whitish  powder. 

A  preliminary  examination  made  with  aqueous,  alcoholic,  and 
ethereal  extracts  of  the  fresh  root,  led  to  the  following  conclusions, 
namely  :  — 

That  the  root  contained  a  bitter  principle  soluble  in  water 
and  alcohol,  but  more  readily  in  the  latter ;  also  a  resinous,  fatty 
matter  and  an  organic  acid,  probably  of  a  fatty  nature,  which  was 
soluble  in  and  extracted  both  by  alcohol  and  ether.  The  probable 
presence  of  gum  and  pectin  was  likewise  indicated,  as  well  as  the 
absence  of  albumen,  sugar,  and  volatile  oil. 

Examination  of  the  Dried  Boot. — A  quantity  of  the  powdered  dried 
root  was  first  treated  with  ether  until  thoroughly  exhausted  by  this 
menstruum,  in  order  to  remove  the  fatty  and  resinous  matter.  The 
ethereal  tincture  had  a  lemon  yellow  colour,  and  left,  on  evaporation, 
a  yellowish  brown  residue,  which  possessed  the  characteristic  odour 
of  the  root,  a  slight  bitter  taste,  was  brittle,  and  had  an  acid  reaction. 


198  YEAR-BOOK   OF    PHARMACY. 

To  dcteT'iniuc  tlio  natiii'c  of  the  free  acid,  the  residue  was  treated 
with  a  weak  solution  of  sodic  carbonate,  and  filtered  from  the  in- 
soluble portion.  To  the  filtrate  a  sufficient  quantity  of  tartaric  acid 
was  added,  when  whitish  oily  globules  were  observed  on  the  surface 
of  the  liquid.  These  had  an  acid  reaction,  possessed  a  disagreeable 
odour,  and  gave  to  paper  a  stain  unafi'ected  by  heat.  The  author 
names  it  megarrhizic  acid.  The  portion  insoluble  in  sodic  car- 
bonate was  treated  with  a  solution  of  caustic  potash,  in  order  to 
effect  the  saponification  of  the  fatty  matter,  and  the  insoluble  resin- 
ous substance  was  removed  by  a  filter,  washed,  dried,  and  reserved 
to  be  examined  subsequently.  To  the  solution  of  soap  obtained  was 
added  a  sufficient  quantity  of  tartaric  acid  to  decompose  it.  Ether 
was  now  added,  and  the  mixture  agitated.  After  a  few  hours  the 
supernatant  ethereal  liquid  was  removed  and  allowed  to  evaporate 
spontaneously,  when  it  was  found  to  possess  properties  character- 
istic of  fatty  acid  bodies.  The  insoluble  resinous  substance  obtained 
before  was  first  boiled  with  water,  then  thrown  on  a  filter,  well 
washed  and  dried.  It  was  afterwards  dissolved  in  ether,  and  the 
solution  decolorized  by  animal  charcoal.  The  filti'ate  was  evapo- 
rated, the  residue  redissolved  in  alcohol,  and  then  allowed  to 
evaporate  spontaneously,  when  it  left  a  deposit  exhibiting  under 
the  microscope  a  rhomboidal  crystalline  structure  ;  it  is  evidently  a 
resin.  This  mefjarrhizitin  is  soluble  in  alcohol  and  ether,  and  is  un- 
affected by  alkalies  and  solution  of  cupric  sulphate. 

The  root,  previously  exhausted  by  ether,  was  next  treated  with 
alcohol  (sp.  gr.  0'835),  until  deprived  of  its  bitter  taste.  The  tinc- 
ture was  evaporated  to  a  small  bulk,  then  thrown  into  water  to 
remove  traces  of  fat  or  resin,  and  afterwards  filtei'ed.  The  liquid 
was  heated  to  expel  the  spirit.  To  the  resulting  aqueous  fluid  was 
added  a  concentrated  solution  of  tannic  acid.  A  bulky,  gelatinous 
precipitate  was  obtained.  This,  being  removed  by  a  filter,  was  well 
washed  and  dried.  It  was  now  dissolved  in  alcohol  (95  per  cent.), 
the  tannin  thrown  down  by  plumbic  subacetate,  the  excess  of  lead 
removed  by  H,  S,  and  the  liquid  filtered  and  evaporated.  The  resi- 
due well  washed  with  ether  yielded  the  bitter  principle  pure.  This 
process  was  adopted  from  that  of  Dr.  "VValtz,  as  mentioned  in  his 
analysis  of  colocynth. 

To  the  principle  thus  obtained  the  name  of  megarrhizhi  is  given. 
It  is  of  a  brownish  coloui",  somewhat  transparent,  brittle,  and  friable, 
yielding  a  yellowish  brown  powder.  It  is  fusible  below  100°  C,  in- 
flammable, more  soluble  in  alcohol  than  in  water,  both  solutions 
being  intensely  bitter.     It  is  insoluble  in  ether.     The  following  re- 


MATERIA    MEDIC  A.  199 

actions  with  reagents  were  obtained :  Hg  S  0.^  dissolved  it  slowly, 
with  the  production  of  first  a  bright  red,  and  afterwards  a  brown 
colour;  H  CI  gave  a  faint  violet  colour ;  H  N  O.,,  a  yellow  dull  colour. 
An  aqueous  solution  of  it  produced  with  ferric  chloride  a  deep 
colour,  but  no  precipitate ;  with  plumbic  acetate  and  subacetate, 
mercuric  chloride,  solution  of  iodine,  potassa  or  its  carbonate,  or 
argentic  nitrate,  no  change ;  with  tannic  acid,  a  bulky,  gelatinous 
precipitate,  and  with  bromine  water,  a  white,  insoluble  precipitate. 
Boiled  with  baryta  water,  decomposition  ensued;  treated  with  dilute 
Hn  S  0.J  or  HCl,  no  change  was  observed  in  the  cold,  but  upon  boiling, 
immediately  decomposition  took  place,  yielding  glucose  and  an 
insoluble  substance,  which  may  be  called  megcvrrhizioretin. 

This  megarrhizioretin,  when  washed  and  dried,  possesses  a  dai'k 
brown  colour,  a  resinous  appearance,  and  is  somewhat  brittle. 
Alcohol  dissolves  it,  but  ether  is  only  a  partial  solvent  of  it,  leav- 
ing an  insoluble  portion  behind.     It  is  therefore  a  complex  body. 

The  ashes  showed,  on  analysis,  the  presence  of  magnesia,  lime, 
iron,  potassa,  soda,  chlorine,  sulphuric  and  phosphoric  acids,  also  a 
silicious  residue. 

It  will  be  seen  from  the  foregoing  that  megarrhizin  belongs  to 
that  class  of  substances  known  as  glucosides,  to  which  belong 
also  colocynthin  and  bryonin,  and  that  it  agrees  with  these  two  in 
many  of  their  chemical  and  physical  properties.  But  megarrhizin 
difiers  from  colocynthin  in  the  fact  that  colocynthein,  the  insoluble 
resinous  substance  obtained  from  the  boiling  of  it  with  diluted 
acids,  is  soluble  in  ether,  while  megarrhizioretin  is  but  partially 
soluble  in  that  liquid,  thereby  agreeing  with  bryoretin.  But  it 
dilfers  from  bryonin  principally  in  the  behaviour  to  sulphuric  acid, 
which  dissolves  megarrhizin,  yielding  a  brown  colour;  while 
bryonin  produces  with  it  a  blue  colour.  Therefore  it  was  concluded 
to  be  a  distinct  principle. 

Physiological  Properties. — A  sample  of  the  extract  prepared  from 
an  alcoholic  tincture,  and  also  some  of  the  bitter  principle,  were 
examined  physiologically,  with  the  following  results : — The  extract 
in  large  doses  is  a  powerful  irritant,  causing  gastro-enteritis  and 
death.  It  produces  griping  pains  in  the  stomach,  nausea,  vomiting, 
and  profuse  diarrhoea,  violent  strangury,  with  other  symptoms  of 
renal  and  vesical  irritation.  Given  in  a  quarter  to  half  grain  doses, 
the  extract  is  a  drastic  hydragogue  cathartic,  causing  nausea,  some- 
times vomiting,  griping  pains,  and  copious  watery  stools.  In  smaller 
doses,  frequently  repeated,  it  is  a  diuretic  and  laxative.  Notwith- 
standing its  activity,  it  is  a  safe  and  convenient  purgative,  and 


200  YEAR-BOOK    OF    PHARMACY. 

useful  in  all  cases  where  it  is  desirable  to  produce  an  energetic 
influence  on  the  bowels,  to  obtain  large  evacuations.  Its  hydragogue 
properties  must  prove  beneficial  in  dropsies.  It  also  augments  the 
urinary  discharges.  In  intestinal  inflammations  it  should  not  be 
used. 

Cortex  Radicis  Granati.  (Pharm.  Zeihmg,  Sept.  23rd,  1876,  659.) 
This  bark  deserves  the  first  place  among  the  remedies  for  tape- 
worm. It  is  true  that  some  practitioners  have  given  it  up  in 
favour  of  konsso,  but  the  cause  of  this  must  be  sought  in  the  age 
of  the  bark  employed  by  them.  The  fresh  bark  only,  and  especially 
that  of  the  roots  of  trees  not  less  than  ten  or  twelve  years  old,  can  be 
thoroughly  depended  upon  for  its  effects.  60-80  grams  of  the  fresh 
bark  should  be  digested  with  750-1000  grams  of  water  for  12  hoxirs, 
then  boiled  for  an  hour,  and  the  decoction  evaporated  to  300  grams. 
The  resulting  strong  decoction  is  mixed  with  30  grams  of  castor  oil 
and  a  sufficient  quantity  of  gum  for  emulsifying  the  oil,  and  the 
whole  taken  first  thing  in  the  morning,  a  suitable  diet  having  been 
observed  during  the  previous  day.  It  is  useful  to  touch  the  worm 
now  and  then  with  a  drop  of  a  mineral  acid  during  its  elimination. 

According  to  an  analysis  by  Cemedella,  the  bark  contains  in  100 
parts  :  wax,  0"8;  resin,  4"5;  mannite,  I'S;  uncrystallizable  sugar,  •2"7 ; 
gum,  32;  inulin,  1"0;  vegetable  mucus,  0"6;  tannic  acid,  10"4;  gallic 
acid,  4"0  ;  extractive,  4'0  ;  malic  acid,  pectin,  calcium  oxalate,  4'5 ; 
cellulose,  51*6.  It  is  occasionally  adulterated  with  the  bark  of 
Berheris  vulgaris.  The  true  root-bark  of  Pnnica  Granahim,  when 
fresh,  is  pale  yellow,  or  greenish  yellow  internally,  and  greyish  yellow 
externally.  To  water  it  imparts  a  yellow  tint,  which  changes  to 
blackish  blue  on  the  addition  of  ferrous  sulphate,  and  to  pink  pass- 
ing to  yellow  on  the  addition  of  acids.  The  stem  bark  and  the 
rind  of  the  fruit  are  useless  as  anthelmintics,  but  possess  tonic  and 
astringent  properties. 

Adulterations  of  the  Rhizomes  of  Imperatoria  Ostruthium. 
(From  Pharmaceut.  Zeitnng,  1877,  224.)  The  rhizomes  of  master- 
wort,  Imperatoria  Ostruthium,  which  were  formerly  officinal  in  the 
Edinburgh  Pharmacopoeia,  and  are  still  so  in  the  Pharmacopceia 
Germanica,  are  liable  to  frequent  and  extensive  adulteration  in  con- 
sequence of  the  careless  and  indiscriminate  manner  in  which  they 
are  collected  in  Switzerland.  The  admixtures  most  frequently 
detected  by  the  writer  wei'e  those  with  aconite  root  and  veratrum 
rhizome.  As  small  particles  of  these  are  more  difficult  to  distin- 
guish from  masterwort  than  the  larger  pieces,  any  such  particles 
which  do  not  permit  of  a  proper  identification  ought  to  be  rejected. 


I 


MATERIA    MEDICA.  201 

Tlie  roots  of  Gentiana  p^mctafa,  Gentiana  purpiirea,  Pimpinella 
saxifraqa,  Meiim  athamanticum,  Libanotis  montana,  and  the  rhizomes 
of  Poh/goimm  Bistorta,  have  also  been  obseiTed  as  occasional  admix- 
tures in  this  drug. 

The  Gums  of  Senegal.  Dr.  A.  Corre.  (Pharm.  Journ.,  from 
Jonrn.  de  Pharm.  [4],  xxiv.,  318.)  In  commerce  the  gums  of  Senegal 
are  distinguished  according  to  the  district  which  yields  them,  or 
the  port  from  which  they  are  exported.  They  are: — (1)  gomjies 
Bas-du-fleuye  (Bas-du-fleuve,  Degana,  and  Podor :  gums  from  the 
desert  of  Bounoun  and  the  country  of  the  Braknas)  ;  and  (2)  Galam 
r,uMS,  or  GOMMES  Haut-du-fleuve  (Galam,  Podor,  Bakel,  and  Medina). 
These  gums,  when  carefully  sorted,  yield  very  different  products, 
■which  the  author  classifies  as  follows : — 

A  first  group  includes  the  gums  in  round  pieces  (en  icndes,  so-called 
because  of  their  form).  The  subdivisions  of  this  group  are  regulated 
by  the  degree  of  consistence  and  resistance,  size  and  colour,  of  the 
balls. 

A.  Hard  Gums  (Gommes  dures),  of  firm  consistence,  with  large, 
clear,  shining  fracture  : — (1)  grosse  blanche  :  pieces  large  or  medium, 
sized,  entire,  white  or  yellowish  white ;  (2)  petite  blanche :  pieces 
small,  entire  or  in  fragments,  generally  whiter  than  the  preceding ; 
(3)  grosse  blonde :  pieces  large  or  medium  sized,  entire,  yellowish  or 
reddish  yellow ;  (4)  petite  blonde :  pieces  small,  entire,  or  in  frag- 
ments, yellowish  or  reddish  yellow ;  (5)  deiircieme  blonde :  pieces 
more  or  less  large,  entire  or  in  fragments,  reddish ;  (6)  fabrique : 
pieces  more  or  less  large,  entire  or  in  fragments,  reddish  or  brownish, 
moderately  limpid,  grumous  or  tearlike  on  the  surface,  with  a  frac- 
ture often  resinoid,  uneven,  and  dull. 

B.  Soft  or  Friable  Gums  (Gommes  molles  ou  friahles). — (7) 
blanche;   (8)  blonde ;   (9)  fabriqite. 

In  a  second  group  the  author  places  the  gums  occurring  in  elon- 
gated masses,  a  form  which  results,  doubtless,  through  delay  in  the 
solidification  of  the  gum  upon  the  tree,  caused  by  rains  or  humidity 
of  the  atmosphere: — (10)  larmeuse:  in  mamillated  or  undulated 
masses,  clear  light  yellow  colour,  shining  at  the  surface,  fracture 
clean,  hard;  (11)  vermicelle :  rather  dull  white,  surface  corrugated, 
fracture  pretty  clean  and  shining,  friable ;  this  gum  is  remarkable 
for  its  convolute  form,  which  resembles  that  of  vermicelli. 

To  a  third  group  belong  the  gums  in  fragments  and  powder,  the 
debris  and  residue  of  the  preceding: — (12)  gj-os  grabeaux ;  (13) 
moyens  grabeaux;  (14)  mentis  grabeaiix ;  (15)  grabeauoi  tries;  (16) 
grabeaux  frabrique ;  (1 7)  poxissiere. 


202  YEAR-BOOK    OF    PHARMACY. 

To  a  fourth  group  is  allotted  (18)  viarrons  or  hois,  a  largisli  gum, 
freqaeutly  of  resinoid  aspect,  yellowish  or  brownish,  mixed  with,  or 
adherent  to,  fragments  of  bark. 

The  Senegal  gums  are  collected  from  a  great  variety  of  plants. 
The  acacias  {Acacia  nilutica,  Verek,  Adansonii,  albida,  dealhata,  Sing, 
Seijal,  etc.)  yield  the  greater  part,  and  the  finest  qualities  They 
are  also  obtained  from  the  Khayd  senegalensis,  certain  Sj)ondias, 
some  Sferculiacece,  and  perhaps  Bassia,  etc. 

As  the  result  of  the  study  of  the  mode  in  which  the  gum  is  pro- 
duced from  the  verek,  the  author  is  of  opinion  that  the  starting- 
point  is  certainly  in  the  cambium.  When  a  transverse  incision  is 
made  in  a  young  branch,  there  is  observed  at  first  a  sort  of  exuda- 
tion, badly  defined,  between  the  wood  and  the  bark.  As  the  exuda- 
tion becomes  more  considerable  it  raises  the  bark,  and  makes  its 
way  to  the  exterior  through  any  cracks  or  fissures.  But  as  there 
are  two  layers  in  this  zone — a  ligneous  and  a  cellular  layer — the 
question  arises  in  which  layer  does  the  gum  take  its  origin  ?  For 
the  followiug  reasons,  the  author  believes  it  to  be  formed  in  the 
ligneous  layer  at  the  expense  of  the  crude  sap  circulating  therein: — 

1.  Upon  difi'erent  specimens  of  verek  he  has  observed  that  at 
the  level  of  the  base  of  the  gummy  exudations  the  exterior  woody 
bundles  become  deviated  in  the  form  of  a  capsule,  and  present  traces 
of  an  erosive  or  destructive  action.  In  very  young  branches,  by  the 
aid  of  a  microscope,  these  bundles  may  be  distinguished,  dissociated 
and  jagged,  in  the  midst  of  the  gummy  matter. 

2.  The  balls  of  gum  are  frequently  marked  with  very  regular 
cavities,  similar  to  those  produced  in  a  viscous  mass  by  blowing  air 
into  it  through  a  slender  tube.  These  cavities  cannot  be  due  to  the 
penetration  of  a  gas  coming  directly  from  without,  for  they  face 
inwards,  i.e.,  towards  the  base  of  the  exudations ;  they  could  only 
be  produced  by  the  air  from  the  vessels  of  the  sap  wood,  ruptured 
and  dissociated  at  the  same  time  as  the  woody  fibres. 

3.  The  mineral  elements  of  gum  (lime,  etc.),  belong  to  the  crude  sap. 
Gum,  however,  is  not  simply  water  charged  with  salts,  neither  is 

it  a  highly  concentrated  saline  solution.  It  is  a  product  that  pre- 
sents great  analogy  of  chemical  composition  with  lignose.  The 
author,  therefore,  considers  gum  to  be  the  result  of  a  kind  of  lique- 
faction of  the  elements  of  the  sap  wood  by  the  crude  sap. 

It  is  incontestable  that  the  formation  of  gum  is  connected  with 
an  anomalous  state  due  to  excess  of  nutrition.  It  is  observed  more 
particularly  at  the  points  of  budding,  and  at  the  bifurcation  of  the 
branches,  and  it  acquires  a  remarkable  development  upon  abnormal 


I 


MATERIA   MEDICA.  203 

nodosities ;  in  fact,  wlierever  the  nutritive  action  exists  in  the 
greatest  intensity.  Beyond  certain  limits,  tliis  energy  in  the  rising 
of  the  sap  is  accompanied  by  a  slackening  of  the  circulation,  which 
leads  to  a  stagnation  of  the  liquid  through  the  engorgement  of  the 
channels  ;  hence,  perhaps  by  absorption,  leading  to  the  softening 
and  liquefaction  of  the  fibrous  and  vascular  element  of  the  sap  -wood. 

In  this  phenomenon  the  easterly  winds  have  a  share,  their  high 
temperature  and  dryness  favouring  the  determination  of  the  sap  to 
the  extei'ior.  Their  influence  is  not,  as  often  stated,  limited  to  the 
production  of  cracks  in  the  bark.  It  will  be  seen  that  there  is  a 
great  analogy  between  the  mode  of  the  formation  of  verek  gum  and 
that  of  the  gum  of  rosacese,  as  described  by  Trecul. 

Recently  an  important  part  in  the  pi'oduction  of  Senegal  gums 
has  been  attributed  to  a  loranthaceous  parasite,  which  is  met  with 
frequently  in  eastern  Africa,  not  only  on  gum  trees,  but  also  on 
guava  trees,  palms,  etc.  The  author  has  never  observed  the  least 
exudation  of  gum  at  the  points  of  implantation  of  this  parasite, 
which  itself  takes  up  sap  and  leaves  no  excess  for  the  plant  on 
which  it  is  developed.  The  nodosities,  which  have  probably  been 
attributed  to  the  action  of  this  parasite,  and  thus  led  to  the  sugges- 
tion, the  author  considers  to  be  the  result  of  insect  punctures. 

The  Preparation  and  Toxic  Effects  of  Gelsemine.  T.  Gr.  Worm  ley. 
(Arner.  Jouni.  Pharm.,  April,  1877,  150.)  The  author  has  formerly 
shown  that  Gelsemium  sempervlrens  contains  an  organic  acid,  gel- 
seminic  acid,  and  a  nitrogenised  alkaloid,  gelsemine,  to  the  latter  of 
which  the  plant  owes  its  activity,  (See  Year-Booh  of  Pharmaoj, 
1876,  194-197.) 

The  method  thei'e  pointed  out  for  the  preparation  of  these  two 
princii^les  was  to  concentrate  the  fluid  extract  of  the  root  (contain- 
ing the  soluble  matter  of  480  grains  of  the  root  to  the  fluid  ounce) 
to  about  one-eighth  its  volume,  dilute  the  concentrated  extract  with 
several  times  its  volume  of  water,  and  after  subsidence  of  the  resinous 
matter  and  filtration,  to  again  concentrate  the  liquid  to  the  original 
volume  of  the  extract  employed.  The  liquid  was  then  acidulated 
with  hydrochloric  acid,  and  the  gelseminic  acid  extracted  with  ether, 
after  which  the  liquid  was  rendered  alkaline,  and  the  gelsemine 
extracted  by  chloroform. 

More  recent  investigations  have  shown  that  by  the  former  part  of 
this  process  a  large  proportion  of  both  the  principles  in  question 
are  separated  with  the  resinous  matter,  and  thus  escape  recovery. 
After  trying  various  methods  for  the  moi'e  complete  recovery  of  these 
principles  from  the  fluid  extract,  the  author  finds  the  following  to 


204  YEAR-BOOK    OF    PHARMACY. 

give  the  best  results.  A  given  volume  of  the  fluid  extract,  acidulated 
■with  acetic  acid,  is  slowly  added,  with  constant  stirring,  to  about 
eight  volumes  of  water;  after  the  separated  resinous  matter  has 
completely  deposited,  the  liquid  is  filtered,  and  the  filtrate  concen- 
trated on  a  water  bath  to  something  less  than  the  volume  of  fluid 
extract  employed.  The  gelseminic  acid  is  then  extracted  from  the 
concentrated  fluid  by  ether,  after  which  the  liquid  is  treated  with 
slight  excess  of  carbonate  of  sodium,  and  the  gelsemine  exti'acted 
with  ether  or  chloroform.  For  the  extraction  of  the  first  of  these 
principles  it  is  not  essential  that  the  liquid  should  be  acidulated, 
but  in  the  presence  of  a  free  acid  the  results  are  more  satisfactory. 

A  series  of  examinations  of  a  number  of  samples  of  the  fluid 
extract  of  gelsemium,  prepared  by  several  of  the  more  prominent 
manufacturers,  showed  that,  as  found  in  commerce,  it  quite  uni- 
formly contains  about  0"'2  per  cent,  of  gelsemine,  and  0"4  per  cent, 
of  the  non-nitrogenised  principle.  The  only  marked  exception  to 
this  was  found  in  the  case  of  a  fluid  extract  furnished  a  physician 
as  a  sample,  which  contained  just  double  the  ordinary  proportion  of 
the  alkaloid  and  acid.  Two  samples  of  fluid  extract,  prepared  by 
the  same  firm,  as  obtained  from  the  shops,  contained  the  ordinary 
quantity  of  the  alkaloid  and  acid.  Within  the  last  few  years, 
thirteen  cases  of  poisoning  by  the  preparation  of  gelsemium,  have 
been  reported,  nine  of  which  proved  fatal.  In  the  fatal  cases  the 
dose  of  the  fluid  extract  varied,  in  the  case  of  adults,  from  about 
one  fluid  dram  to  one  tablespoonful  ;  and  the  time  of  death  from 
two  hours  and  a  half  to  seven  hours  and  a  half.  In  one  instance  15 
grains  of  the  resinoid  "  gelsemin,"  proved  fatal  to  a  woman  in  one 
hour  after  the  dose  had  been  taken. 

Fifty  minims  of  a  tincture  prepared  from  four  ounces  of  the  root 
to  one  pint  of  dilute  alcohol,  proved  fatal  to  a  child  aged  three 
years  in  two  hours.  And  in  another  instance  a  much  less  quantity 
of  the  tincture,  taken  in  two  doses,  caused  the  death  of  a  child  in 
one  hour  after  the  second  dose  had  been  taken. 

In  one  of  the  non-fatal  cases  a  tablespoonful  of  the  fluid  extract 
had  been  taken  ;  but  it  was  soon  followed  by  vomiting,  induced  by 
an  emetic. 

In  another  instance,  in  which  from  one  to  two  teaspoonfuls  of 
the  ordinary  fluid  extract  produced  most  profound  symptoms, 
recovery  took  place  under  the  administration  of  three  grains  or 
more  of  morphia,  employed  hypodermically,  in  half -grain  doses, 
repeated  every  few  minutes.  From  the  report  of  this  case  by  Dr. 
Geo.  S.  Courtwright  {^Cincinnati  Lancet  and  Observer,  Nov.,  1876), 


MATERIA    MEDICA.  205 

it  would  appear  that  the  morphia  was  the  means  of  saving  the  life 
of  the  individual. 

In  the  cases  thus  far  reported  there  seems  to  be  only  one,  or  at 
most  two,  instances  in  which  the  poison  was  administei'ed  with 
criminal  intent. 

The  Active  Principles  of  Calabar  Bean.  (Pharm.  ZeU.,  1877, 
Nos.,  16,  30;  Neiv  Remedies,  June,  1877,  103.)  There  is  scarcely 
another  modern  di-ug  which  has  been  subjected  to  such  frequent 
and  exhaustive  investigations  as  the  seeds  oi  Physostigmavenenosum; 
bat  at  the  same  time  there  is  a  surprising  difference  of  views  and 
theories  in  regard  to  its  physiological  action.  All  authors  are  agreed 
on  one  property  of  the  drug,  namely,  that  of  contracting  the  pupil, 
but  in  all  other  respects  they  differ  widely.  Ever  since  Fraser's 
classical  investigations  (1863),  it  has  been  customary  to  regard  the 
calabar  bean  as  a  poison  directly  paralysing  the  spinal  cord,  and 
from  this  view  arose  its  employment  as  a  remedy  in  tetanus,  where 
it  was  found  (by  Watson  and  others)  to  be  so  exceedingly  effective 
that  most  other  previously-used  remedies  were  henceforth  dis- 
carded. But  lately  statements  have  been  published,  in  reference  to 
the  action  of  the  commercial  extract  of  calabar  and  of  "  physos- 
tigmin,"  which  would  make  their  usefulness  in  tetanus  appear 
exceedingly  problematical.  Rossbach  and  Nothnagel,  for  instance, 
assert  that  extract  of  calabar  is  not  a  paralyzing  but  a  tetanizing 
poison ;  and  the  latter  adds  that  it  resembled  strychnia,  in  so  far  as 
its  paralysing  effect  was  a  secondary  symptom  depending  upon  an 
exhaustion  of  nerves  and  muscles,  by  preceding  violent  convulsions. 
Martin  Damourette  thought  he  had  solved  the  problem  by  supposing 
that  the  drug  excited  the  spinal  mari-ow,  and  paralysed  the  peripheral 
nerves.  But  such  compromises,  unsupported  by  evidence,  are  in- 
admissible in  exact  science,  and  Rossbach  was  unable  to  obtain  any 
paralysing  effects  upon  the  peripheral  nerves  with  Merck's  physos- 
tigmin.  It  was  left  to  chemistry  to  throw  light  upon  these  apparent 
discrepancies.  Hitherto  it  had  been  supposed  that  calabar  contained 
only  o/ie  alkaloid,  namely,  physostigmia,  as  Hesse  called  it,  or  eserina, 
as  Ve  and  Leven  termed  it.  But,  according  to  the  researches  of 
Harnack  and  Witkowsky,  conducted  in  the  pharmacological  labora- 
tory at  Strassbourg,  calabar  bean  contains  tivo  alkaloids,  one  of 
which  entirely  resembles  strychnia  in  its  effects,  while  the  other 
produces  the  previously  known  central  paralysis.  The  new  alkaloid, 
named  by  the  discoverers  calabarin  (calabaria),  differs  from  phy- 
sostigmia by  its  insolubility  in  ether,  and  easier  solubility  in  water  ; 
it  is  also  soluble  in  alcohol.     A  farther  difference  is  the  fact  that 


206  YEAR-BOOK    OF    PHARMACY. 

the  precipitate  produced  by  potassium  iodobydrargyrate  in  calabarin 
solutions  is  insoluble  in  alcohol.  The  commercial  preparations  of 
calabar  are,  according  to  the  same  authorities,  mixtures  of  the  two 
alkaloids  in  varying  proportions,  and  therefore  produce  such  dis- 
cordant effects.  Whenever  physostigmia  preponderates,  it  appears 
to  suppress  the  effects  of  calabarin.  This  fact  explains  why  most 
investigators  merely  took  notice  of  the  paralysing  effects.  On  the 
other  hand,  there  are  preparations  in  the  market  which  scarcely  con- 
tain any  physostigma  at  all,  as  was  proved  directly  by  Harnack  and 
Witkowsky  in  the  case  of  an  English  specimen.  The  purest  com- 
mercial preparation  was  Duquesnel's  eserine,  which  appears  to  be 
absolutely  free  from  calabarin.  Since,  therefore,  commercial  pre- 
parations of  calabar  may  contain  comparatively  large  per  centages 
of  calabai'in,  the  administration  of  which  is  positively  injurious  and 
highly  dangerous  in  tetanus,  it  is  desii'able  to  possess  a  means  of 
control,  or  to  employ  preparations  which  make  the  pi'esence  of  the 
dangerous  alkaloid  impossible.  As  the  latter  is  absolutely  insoluble 
in  ether,  it  appears  advisable  to  introduce,  in  place  of  the  present 
officinal  alcoholic  extract  of  calabar,  an  ethereal  extract,  although  the 
same  drawback,  which  Hager  points  out  as  inhering  to  the  officinal 
preparation,  is  not  unlikely  to  attach  to  this,  namely,  a  process  to 
speedy  deterioration.  Indeed,  physostigmia  is  very  readily  decom- 
posed with  formation  of  Duquesnel's  rubeserin,  which  appears  to 
be  formed  not  only  under  the  influence  of  alkalies,  but  even  spon- 
taneously, as  may  be  suspected  from  the  change  of  colour  observable 
in  old  calabar  beans.  Duquesnel's  eserine  has  an  especial  tendency 
towards  this  decomposition,  according  to  Harnack  and  Witkowsky. 
But  rubeserin  cannot  contaminate  the  ethereal  extract  prepared 
from  the  beans,  since  it  is  insoluble  in  ether. 

In  No.  21  of  the  same  seinal  we  find  a  communication  by  0.  Hesse, 
commenting  on  the  above  article,  in  which  he  states  that  he  has 
succeeded  in  extracting  from  calabar  beans  a  substance  crystal- 
lizing from  alcohol  in  probably  the  same  form  as  the  so-called 
crystallized  eserine,  and  appearing  to  be  a  much  more  definite  and 
stable  substance  than  the  latter.  It  crystallizes  from  ether,  chloro- 
form, and  petroleum  ether  in  white  silky  needles,  melts  at  133- 
134°  C,  is  indifferent,  and  greatly  reseaibles  cholesterin  and  iso- 
cholestcrin  in  appearance,  though  not  in  properties  or  composition. 
Hesse  also  adds  that  the  substitution  of  nn  ethereal  instead  of  an 
alcoholic  extract  would  be  of  but  little  use,  as  calabar  beans  contain 
physostigmia  in  such  a  combination  that  it  appears  insoluble  in  and 
incapable  of  extraction  by  pure  ether. 


MATERIA    MEDICA.  207 

Tlie  Tvell-known  mannf.actnring  chemist,  E.  ]\Ierck,  in  Darmstadt, 
has  heretofore  prepai'od  and  sohi  a  substance  which  was  supposed 
to  be  the  only  active  principle  of  calabar,  and  which  he  called  cnla- 
barin,  but  which  was  really  eserine  or  physostigmin.  He  now 
accepts  and  confirms  the  results  of  Harnack's  and  Witkowsky'.s 
researches  ;  and  has  introduced  both  of  the  active  principles  into  the 
market  labelled  with  their  correct  names,  namely,  j^hysosfigmin  (or 
eserine,  being  the  same  substance  which  he  formerly  sold  as  cala- 
barin),  and  calabarin,  distinguished  by  the  addition  of  Harnack's 
name  ("  Harnack's  Calabarin.")  The  attention  of  ijhysicians  and 
pliarmadsts  is  2iarticnlarh/  directed  to  this  change  of  ajypellations. 

Carobse  Folia.  Dr.  A.  Alt.  (Pharmaceut.  Zeitmig,  1877,  289.) 
The  author's  attention  was  directed  to  this  drug  by  Mr.  C.  Weber, 
whose  long  experience  as  an  apothecary  at  Rio  de  Janeiro  and  Monte 
Video  had  made  him  familiar  with  its  valuable  therapeutic  properties. 
It  is  used  in  Brazil  as  a  diaphoretic,  diuretic,  and  tonic  ;  but  chiefly 
and  most  successfully  as  an  alterative  in  the  various  forms  of  syphilis. 
The  author  has  tried  it  extensively,  and  expresses  himself  much 
pleased  with  the  results,  especially  in  old  standing  cases  of  syphilitic 
eruptions,  and  after  a  course  of  mercurial  treatment. 

The  drug  is  known  under  the  name  "  Caroba  "  in  Brazilian  com- 
merce, and  has  hitherto  met  with  little  attention  in  Europe.  It 
consists  of  long  ovate  leaflets,  which  are  dark  green  on  the  upper 
and  pale  green  on  the  lower  surface,  and  have  very  conspicuous 
lateral  veins.  Its  botanical  source,  according  to  Spreugel,  is  Jaca- 
randa  procera,  a  tree  belonging  to  the  family  Bignoniaceoi,  and 
growing  to  a  height  of  thirty  to  forty  feet.  Its  root  is  dark  red  ex- 
ternally, and  whitish  yellow  internally  ;  its  stem  is  much  branched, 
and  densely  covered  with  unequally  pinnate  leaves.  The  flowers 
vary  in  colour  between  white  and  red,  and  emit  a  pleasant,  honey- 
like odour  ;  the  fruit  is  a  two-celled  woody  capsule.  The  drug  was 
introduced  to  the  notice  of  European  practitioners  by  Dr.  Joan 
Alves  de  Carneiro,  who  placed  it  before  the  Medical  Academy  of 
Paris.  The  experiments  conducted  with  it  by  Carron  de  Villards, 
Bompani,  Souto,  Barros  Pimental,  Level,  Spicks,  and  Martin,  the 
last  named  of  whom  called  the  plant  "  Cyhistas  antisyphilitica'^ 
proved  veiy  successful.  A  decoction  of  the  leaves  is  much  used  bv 
the  natives  as  a  stomachic  tonic  and  for  improving  the  appetite.  In 
syphilis  and  in  skin  diseases  the  drug  is  employed  both  internally 
and  externally.  The  preparations  generally  used  are  the  decoction 
and  the  powdered  leaves.  The  author  recommends  a  liquid  hydro- 
alcoholic  extract  containing  three  to  four  per  cent,  of  dry  extract. 


20S  YEAR-BOOK    OF    PHARMACY. 

Tiinbo.  M.  Martin.  (New  Beviedies,  from  Bull.  Gen.  de  Therap.) 
Plants  belonging  to  tlie  Stxpindacece,  the  same  to  which  PaulUaia 
sorhilis  (the  botanical  source  of  guarano)  belongs,  are  very  common 
in  Brazil,  and  comprise  both  trees  and  climbing  shrubs.  Some  have 
such  poisonous  properties  that  the  natives  use  their  juices  as  arrow- 
poisons,  while  others  are  innocuous  or  simply  narcotic.  The  timbo 
(PaidUnia pinnata,  Lin.)  belongs  to  the  latter  class.  The  timbo  is 
a  tree  found  in  Brazil,  Mexico,  the  Antilles,  and  in  Guiana.  The 
leaves  are  composed  of  five  leaflets,  oval,  lanceolate,  and  crenulated. 
The  flowers  are  polygamous,  dioecious,  and  have  five,  or  rarely  four 
pai'ts ;  an  imbricate  calyx  ;  four  unequal  petals  furnished  with  scaly 
appendices  ;  eight  stamens  situated  around  a  disc  with  notched 
edges ;  ovary  with  three  cells,  surmounted  with  three  styles,  and 
containing  three  seeds,  and  commonly  one  which  has  aborted,  which 
is  provided  with  an  arillus  and  contains  under  its  envelope  an 
embryo  without  albumen.  The  bark  of  the  timbo  root  is  the  only 
part  used  in  Brazil;  it  is  of  a  yellowish  grey  colour,  and  variable  in 
length  and  thickness.  In  transverse  sections  there  is  observed  from 
outside  inwards  :  (1)  An  exterior  layer  of  periderm,  composed  of 
numerous  masses  of  corky  or  woody  tissue ;  (2)  on  reaching  the 
central  parenchyma,  there  are  seen  here  and  there  small  masses  of 
hardened  cells  (that  is  to  say,  having  early  incrustations), — this 
element  is  frequent  in  the  bark  and  in  this  situation ;  (3)  a  very 
thick  layer  of  cortical  parenchyma,  in  which  the  cells  are  distended 
with  starch  ;  (4)  in  the  midst  of  this  parenchyma  cells  containing 
a  resinous  material ;  (5)  bundles  of  liber  arranged  in  interrupted 
lines  and  mixed  with  rays  of  the  medulla.  This  bark  is  Avithout 
difiiculty  reduced  to  powder.  Five  grams  of  it  will  absorb,  cold, 
fifteen  grams  of  distilled  water. 

The  bark  of  timbo  root  has  an  agreeable  aromatic  odour,  slightly 
resembling  musk.  In  Brazil  it  is  only  employed  externally.  Poul- 
tices are  made  from  it  with  boiling  water,  which  are  applied  to  the 
side  in  afiections  of  the  liver.  It  often  causes  intense  eruptions,  in 
which  case  the  application  is  discontinued. 

M.  Martin  has  isolated  from  the  root-bark  starch,  resin,  an  essen- 
tial oil,  chlorophyll,  tannin,  an  organic  acid,  traces  of  glucose,  and 
an  alkaloid  to  which  he  gives  the  name  of  "  timbouiue." 

By  first  treating  the  finely  powered  bark  by  carbon  disulphide, 
the  extraction  of  the  alkaloid  and  other  principles  is  facilitated. 
The  sulphate  of  timbonine  crystallizes  in  white  needles. 

Note  on  a  Piper  Jaborandi  from  Rio  Janeiro.  Dr.  A.  Gubler, 
(Journ.  de  Pharm.  et  de  Chim.  [4],  xxv.,  12b;   Pharmaceut.  Journ. 


MATERIA    MEDICA.  209 

3rd  series,  vii.,  7ol.)  Besides  the  jaborandi  of  Dr.  Coutlnho  (Pilo- 
carpus jmnnatif alius) ,  the  sialogogue  and  sudorific  properties  of 
which  are  so  remarkable,  there  exists  in  Brazil,  as  is  known,  a  large 
number  of  plants  bearing  the  same  popular  name,  which  are  used 
against  the  bites  of  serpents,  etc.  All  the  botanical  species,  however, 
are  included  in  two  families,  Butacece  and  Piperacece.  Among  the 
latter.  Piper  citrifolium  and  P.  reticidatum  have  been  mentioned  as 
particularly  efficacious.  A  jaborandi  from  the  province  of  Rio 
Janeiro,  which  has  been  the  subject  of  a  note  in  the  Journal  de 
Therapeutique,  for  November  25th,  by  Professor  Gubler,  appears  to 
be  referable  to  either  of  these  species,  which  perhaps  should  be  com- 
bined in  one. 

The  plant  is  a  shrub,  usually  attaining,  but  sometimes  consider- 
ably exceeding,  a  metre  in  height.  The  stems  are  fasciculated  at  the 
base,  simple,  and  denuded  for  half  their  length,  cylindrical,  very 
straight,  and  articulated  like  the  bamboo;  towards  the  top  they  bear 
dark  green  leaves  that  are  alternate,  shortly  petiolate,  oval-lanceo- 
late or  slightly  obtuse.  In  the  axils  of  these  are  sometimes  found 
catkins  of  male  flowers.  A  supply  of  the  plant  collected  by  Dr.  da 
Veiga,  of  the  Brazilian  navy,  has  been  investigated  chemically, 
physiologically,  and  therapeutically. 

According  to  Professor  Gubler  the  entire  plant  exhales  a  slightly 
aromatic  odour,  which  becomes  more  pronounced  upon  bruising  the 
leaves  between  the  fingers.  When  chewed  the  taste  is  at  first 
slightly  acid,  then  warm  and  aromatic,  and  finally  very  piquant,  and 
comparable  to  that  of  pyrethrum  root.  This  taste  is  met  with  in 
the  stems  and  especially  in  the  roots,  where  it  attains  a  high  degree 
of  intensity,  chiefly  in  the  moderately  large  portions,  about  the  size 
of  a  crow  quill,  which  are  externally  of  a  rather  decided  grey  colour. 
The  more  slender  and  whitish  portions  are  rather  insipid,  and  the 
finest  have  hardly  any  taste  at  all.  These  differences  are  dependent 
upon  the  constitution  and  thickness  of  the  cortical  layer,  which 
appears  to  be  the  seat  of  the  active  principle. 

When  a  picked  fragment  of  the  root  is  chewed,  at  first  no  sensa- 
tion is  produced  on  the  palate  ;  the  prickling  is  first  manifested  at  a 
short  interval  after  the  vegetable  tissue  becomes  impregnated  with 
saliva.  It  would  appear  that  the  active  principle  of  the  drug  does 
not  exist  ready  formed  in  the  plant,  but  is  due  to  a  special  fermen- 
tation "in  the  presence  of  water,  similar  to  that  which  sets  free  oil 
of  bitter  almonds  or  oil  of  mustard.  When  once  manifested  the 
piquancy  rapidly  acquires  great  energy,  being  accompanied  by  pain- 
ful shootings  and  vibratory  tremblings  of  the  tongue  and  lips,  as 

P 


210  YEAR-BOOK    OF    PHARMACY. 

though  these  organs  were  traversed  by  an  electric  discliarge.  At 
the  same  time  a  very  active  secretion  of  all  the  buccal  glands 
becomes  developed,  and  especially  an  extraordinarily  abundant  sali- 
vation. These  phenomena  persist  for  a  few  moments  after  the 
sapid  pulp  has  been  rejected,  but  then  decrease  and  disappear, 
leaving  a  sensation  of  freshness  and  a  certain  degree  of  anee.sthesia 
of  the  palate.  After  a  few  minutes,  however,  all  the  parts  return  to 
their  normal  state. 

Upon  swallowing  the  saliva  charged  with  the  active  principle,  an 
impression  of  heat  is  produced  at  the  back  of  the  throat,  which 
extends  to  the  oesophagus  and  stomach,  where  it  gives  rise  to  a  sen- 
sation resemblino:  huno^er. 

The  chemical  composition  has  been  studied  by  M.  Hardy,  who  in 
some  preliminary  experiments  with  infusions  was  able  to  demon- 
strate the  presence  of  an  alkaloid. 

Some  leaves  and  stalks  were  therefore  powdered  and  left  tu 
macerate  for  four  days  with  three  times  their  weight  of  90^  alcohol, 
acidulated  with  eight  grams  of  hydrochloric  acid  per  litre.  The 
alcohol  was  then  decanted  and  fresh  alcohol  added,  and  this  was 
repeated  three  times.  The  alcoholic  solutions  were  concentrated  by 
distillation,  and  the  aqueous  solution  evaporated  and  decomposed 
by  ammonia  in  the  presence  of  excess  of  chloroform.  Upon  evapo- 
ration of  the  chloroform  the  base  was  left  free,  but  still  impure.  It 
was  therefore  treated  with  water  acidulated  with  hydrochloric  acid, 
which  dissolved  the  major  part  of  it ;  the  solution  was  filtered,  eva- 
porated, and  ag  lin  decomposed  by  ammonia  in  the  presence  of 
excess  of  chloroform.  Upon  evaporation  of  the  chloroform  solution 
the  base  was  deposited,  having  a  crystalline  appearance  and  slightly 
yellowish  tint. 

The  base  presents  the  characteristic  reaction  of  alkaloids ;  its 
solution  gives  a  white  precipitate  with  iodide  of  mercury  and  potas- 
sium, and  with  iodine  in  iodide  of  potassium.  Another  portion  of 
the  leaves  was  distilled  with  water  to  obtain  the  volatile  oil,  but 
only  a  small  quantity  was  collected,  insuffijient  for  investigation. 

The  alkaloid  dissolved  easily  in  water  slightly  acidulated  with 
hydrochloric  acid,  and  such  a  solution  was  used  by  Dc.  Bochefon- 
taine  to  study  its  physiological  action  upon  animals.  He  found 
that  it  did  not  act  upon  the  heart,  or  influence  the  muscular 
contractility  ;  it  was  not  a  convulsivant.  It  appeared  to  have  the 
]iower  to  prevent  the  mechanical  or  electric  excitations  of  the 
mixed  nerves,  such  as  the  sciatic,  from  being  transmitted  to  the 
muscles.     It  appeared  even  to  postess  the  parahsing  power  at  the 


MATERIA    MEDiCA.  211 

outset,  and  this  property  would  seem  to  distiuguisU  it  from  curare. 
Indeed,  the  paralysing  aetion  of  curare  is  usually  preceded  by  some 
slight  spasmodic  movements,  which  have  not  been  observed  in  frogs 
poisoned  with  the  alkaloid  of  false  jaborandi. 

Professor  Gubler  remarks  that  the  effects  observed  after  the  admin- 
istration of  the  plant  to  the  human  subject,  although  in  small  doses, 
had  not  led  him  to  expect  so  violent  an  action  from  the  alkaloid  of 
the  Rio  piper.  The  first  experiment,  in  1875,  with  the  compara- 
tively fresh  plant,  did  not  reveal  any  great  activity  compared  with 
the  excessive  power  of  Pilocarpus  penaatifulius.  Besides  the  peppery 
sensation  on  the  mouth  and  throat,  and  the  heat  in  the  stomach, 
doses  of  four  to  six  grams  of  the  leaves  in  infusion  only  caused 
slight  salivation  and  diaphoresis.  More  recent  experiments  have 
been  still  less  fruitful.  In  a  case  of  acute  albuminous  nephritis  its 
effects  were  absolutely  nil ;  whilst  in  the  same  patient  on  the  follow- 
ing day  an  infusion  of  four  grams  of  Pilocarpus  jaborandi  in  20U 
grams  of  water  caused  abundant  salivation  and  sweating,  and  an 
increased  excretion  of  urine. 

From  these  negative  facts  Professor  Gubler  draws  the  following 
conclusions  : — 

1.  That  there  exists  a  striking  difference  between  the  mode  of 
action  of  Pilocarpus  pennatifolius  and  of  Piper  reticulatum.  With  an 
insignificant  topical  action,  the  Pilocarpus  manifests  a  diifused  action 
of  great  energy  ;  the  second,  though  very  aggressive  to  the  organs 
at  the  entrance  to  the  j^rimce  vioi,  appears  to  be  nearly  inert  when  ic 
once  enters  the  circulation. 

2.  That  this  inertia  of  the  Piper  is  more  apparent  than  real,  and 
due  to  the  insufficiency  of  the  doses  employed.  In  future  it  will  be 
desirable  to  administer  larger  doses  of  the  leaves,  or  better  still  of 
the  root,  to  obtain  physiological  effects. 

But  if  the  alkaloid  discovered  by  M.  Hardy  is  a  certain  test  of 
the  efficiency  of  the  Pipjer  reticulaluni,  the  experiments  of  M.  Boche- 
fontaine  show  that  it  will  be  advisable  not  to  seek  to  obtain  the  first 
manifestations  through  the  secretions,  as  the  new  agent  is  a  poison 
of  the  motor  system  closely  allied  to  curare. 

Rssina  Gaaiaci  Peruviana,  Aromatica  vel  Oiorata.  A.  Kopp. 
(Arcliiu  der  PJiarmacie,  Sept.,  1876.)  Some  time  ago  the  firm  of 
Gehe  &  Co.  purchased  a  resin  in  Paris  which  they  have  since  been 
selling  to  perfumers,  and  the  origin  of  which  could  not  be  ascertained. 
It  is  entirely  difi"orent  from  true  guaiac  resin,  yields  in  distillation 
with  water  about  4  per  cent,  of  volatile  oil,  having  an  odour  resem- 
bling a  mixture  of  peppermint  and  citron,  and  yields  in  dry  disLil- 


212  YEAR-BOOK    OP    PHARMACY. 

lation  various  oils  of  different  boiling  points,  -whicli  exhibit  very 
peculiar  colours.  The  portions  distilling  below  210°  C.  were 
brownish  yellow  to  brown,  strongly  dichroic,  and  became  green 
■with  ferric  chloride.  Addition  of  aqueous  ammonia  or  soda  turns 
them  deep  red,  the  ammonia-water  itself  becomes  red,  and  on 
neutralization  with  an  acid  changes  to  blue.  The  portion  boiling 
between  255°  and  270°  distils  over  of  a  pure  and  deep  azure  colour, 
resembling  ammonio-cupric  solutions.  This  is  probably  identical 
with  the  blue  oil  of  matricaria  and  galbanum. 

Tayuya.  (Pharm.  CenfralhaUe,  1877,  211.)  A  previous  notice  of 
this  drug  will  be  found  in  the  Year-Boole  of  Pharmacy,  1876,  167. 

Tayuya  or  tayuia,  is  the  name  of  a  vegetable  drug  which  has  been 
employed  for  a  very  long  time  by  the  natives  and  physicians  of 
Brazil,  as  a  remedy  in  various  diseases.  Taijuia  de  ahohrinha,  or 
ahobra,  is  the  common  name  of  the  plant  in  question,  which  is  Der- 
mophyUa  pendulina,  Manso,  nat.  fam.  Cucurbitaceas-Bryonieae,  and 
whose  synonyms  are  Brianosperma  Jicifolia,  Mart.,  Bryonia  ficifolia, 
Lam.,  Bryonia  tayuya,  Velloso.  The  root  is  the  most  active  portion. 
It  is  said  to  be  a  most  valuable  remedy  in  malarious  fevers,  dropsy, 
syphilis,  mental  disorders,  elephantiasis,  skin  diseases,  etc.  It  has 
also  been  used  with  tolerable  success  externally,  in  form  of  a  lotion, 
particularly  in  an  affection  common  to  Brazil,  namely  an  inflammation 
of  the  sphincter  ani  (bicho  do  cu),  according  to  Rosenthal,  in  his 
"  Synopsis  Plantarum." 

Stanislaus  Martin  states  (in  L" Union  Pharm.')  that  he  had  received 
specimens  of  the  root  in  slices  5  cm.  (2  inches)  broad  and  2-3  mm. 
(about  \  inch)  long.  According  to  Martin's  description,  it  does  not 
seem  to  be  much  different  from  that  of  the  European  Bryonia 
root.  He  extracted  from  it  a  green  resin  (tayuyin) ;  a  citron- 
yellow  fat,  and  brown  extractive  matter,  both  of  very  bitter,  aromatic 
taste ;  tannin,  pectin,  traces  of  glucose,  starch,  and  volatile  oil ;  and 
he  found  the  ash  to  contain  magnesia,  lime,  alumina,  potassa,  and 
iron.  He  could  find  no  alkaloid  in  it.  Prof.  Luigi  Gabba,  of  Milan, 
extracted  the  root  with  alcohol,  and  obtained  by  evaporation  a  brown 
extract,  of  neither  acid  nor  alkaline  reaction,  very  stable,  and  drying 
up  to  an  amorphous  mass,  which  -was  only  partially  soluble  in  cold, 
but  more  so  in  boiling  water.  The  latter  solution,  mixed  with  dilute 
sulphuric  acid  and  heated,  did  not  exhibit  any  remarkable  change, 
but  gave  indications  of  glucose.  As  this  reaction  failed  to  make  its 
appearance  before  the  addition  of  the  acid,  Gabba  concluded  that  the 
root  contained  a  glucoside.  Prof.  Zenoni  states,  that  on  exhausting 
the  root  with  ether  and  then  treating  it  with  acidified  alcohol,  he 


I 


MATERIA    MEDIC  A.  213 

obtained  a  substance  which  appeared  to  give  him  the  reactions  of  an 
alkaloid.  Yvon,  who  subjected  Martin's  investigation  to  a  control, 
found  in  it  a  wax-like  resin,  soluble  in  ether  and  chloroform,  of  acid 
reaction,  greenish  yellow  colour,  and  very  bitter  taste.  Its  melting- 
point  is  said  to  be  at  49°  C.  (120°  F.),  and  its  solution  in  alkalies  or 
ammonia  developed  microscopic  crystals.  This  resin  is  said  to  be 
the  active  portion.  An  alcoholic  tincture  of  the  root  deposited,  after 
concentration,  a  small  qaantity  of  prismatic  crystals,  but  they  were 
devoid  of  alkaloidal  properties. 

The  explorer  Luigi  Ubicini  brought  the  root  to  Europe,  and  caused 
a  strong  tincture  to  be  prepared  from  it,  of  the  strength  of  1  part 
dry  root  to  3  parts  of  80  per  cent,  alcohol.  This  was  directed  to 
be  diluted  with  3  times  its  weight  of  dilute  alcohol  before  using, 
and  this  diluted  tincture  is  used  internally,  as  Tlnctura  Dermophyllce 
diluta,  in  doses  of  2  to  12  drops,  3  to  4  times  a  day.  The  daily  dose 
should  not  exceed  24  drops.  For  external  use  in  syphilitic  or 
scrofulous  skin  diseases,  it  is  to  be  diluted  with  twenty  or  thirty 
times  its  weight  of  water;  although  it  maj'  be  used  in  concentrated 
form  upon  indui'ated  glands.  For  hypodermic  use  03-0"5  gram  of 
the  tincture  are  to  be  diluted  with  water  to  1  gram,  which  constitutes 
one  dose. 

Note  on  Dickamali  Resin.  Professor  Fliickiger.  (Pharm. 
Juurn.  3rd  series,  vii.  589.)  This  substance,  the  resinous  exudation 
of  Gardenia  lucida,  Roxb.,  Bubiacece,  is  much,  used  in  India,  both 
internally  and  externally.  It  contains,  according  to  Stenhouse,  a 
crystallizable  resin,  described  by  this  chemist  "as  one  of  the  most 
beautiful  substances  of  that  kind."  It  has  a  marked,  peculiar  odour, 
somewhat  resembling  rue  and  aloes  ;  it  looks  crystalline  and  has  a 
yellowish  colour,  being  decidedly  yellow  when  powdered ;  the  solu- 
tion has  a  fine  yellow  colour  with  a  greenish  hue.  It  assumes  an 
intensely  greenish  brown  colour  on  addition  of  ferric  chloride,  and 
on  addition  of  a  little  soda  it  turns  brown.  It  belongs  to  the 
aromatic  class  of  organic  compounds,  as  it  yields,  by  fusing  with 
caustic  potassa,  protocatechuic  acid. 

Indian  Hemp  and  its  Active  Principle.  (Pharm.  Zeit.  fUr  Buss., 
1876,  705;  New  Bemedies,  March,  1877.)  The  home  of  hemp  is 
Persia  and  the  high  plateau  of  northern  India,  whence  it  has  gradually 
spread  to  other  countries,  so  as  to  be  domesticated  everywhere. 
Its  narcotic  properties,  however,  are  only  developed  fully  in  its 
native  home  in  Asia,  and  in  certain  parts  of  Africa,  where  it  is  used 
as  a  narcotic  stimulant  and  intoxicant  by  nearly  300,000,000  of 
inhabitants. 


214  year-book:  of  prarmact. 

A  preparation,  called  madjonn,  is  sold  in  Alc^iors,  -nliich  is  pow- 
dered Ca7uinhis  safira  boiled  with  honey  for  a  lonGfor  or  shorter 
time,  according  to  the  desired  consistence.  Usually  it  is  kept  mixed 
with  a  certain  portion  of  raa-el-lianoiif,  a  spice  compound  contain- 
ing nutmeg,  cinnamon,  cloves,  various  peppers,  ginger,  galangale, 
and  Guinea  grains.  This  mixture  is  also  called  Iclf.  The  dose  varies 
from  the  size  of  a  hazel  nut  to  that  of  a  walnut,  according  to  the 
acre,  sex,  and  tolerance  of  the  person  using  it.  ]\rost  eaters  of 
hashish  also  smoke  the  dried  leaves  of  the  plant,  either  alone  or 
mixed  with  the  so-called  "  tobacco  of  the  desert,"  which,  according 
to  Dr.  Gnyon,  is  a  species  of  hyoscyamus. 

Dr.  Preobraschensky,  who  accompanied  the  expedition  to  Chiwa 
in  187o,  furnishes  the  following  information  on  the  hashish  of  Cen- 
tral Asia: — "This  article  occurs  in  the  bazaars  of  large  cities  of 
^riddle  Asia  in  the  form  of  plates  or  cakes  of  various  shapes,  mostly 
five  to  fifteen  inches  long,  five  to  ten  inches  broad,  and  one  to  three 
inches  thick  ;  externally  they  are  dark  brown,  internally  greenish 
or  brownish,  of  firm  consistence,  very  tough,  and  almost  incapable 
of  being  broken,  but  easily  cut  into  fine  shavings.  They  are  pre- 
pared as  follows  :  The  resinous  juice  from  the  fresh  unripe  flower- 
tops  is  collected  during  spring,  mixed  with  sand  and  water  to  a 
doughy  mass,  which  is  spread  upon  a  surface  of  clay,  and  dried 
until  it  can  be  curt  with  a  knife  into  plates.  In  a  few  days  more  the 
excess  of  water  has  evaporated  and  the  substance  is  ready  for  use. 
It  is  called  hashish  by  the  Russians,  nascha  hy  the  natives,  bang 
and  gunjah  by  the  Persians,  and  is  exported  from  Bochara  to  Chiwa, 
Tashkend,  Kokant  (Chokand),  and  other  places. 

The  active  principle  of  hashish  has  been  supposed  to  be  resin. 
Dr.  Preobraschensky  has,  however,  lately  subjected  hashish  to  a 
chemical  analysis,  and  has  found  an  alkaloidal  body  not  only  in  tho 
commercial  substance,  but  also  in  the  flower-tops  of  hemp  itself, 
and  the  pure  extract  prepared  from  it,  which  was  recognised  as 
nicnfine.  150  grams  of  the  herb,  distilled  with  water,  furnished  2.V-1- 
milligrams  of  nicotine  ;  50  grams  of  the  herb,  distilled  with  caustic 
lime  and  potassa,  yielded  335-28  milligrams;  5  grams  of  the  ex- 
tract of  Cannabis  indica,  dissolved  in  alchohol  and  distilled,  yielded 
a  distillate  containing  91"14  milligrams  of  nicotine  ;  and  2  grams  of 
the  extract,  distilled  with  caustic  lime  and  potassa,  furnished  63"'> 
milligrams  of  the  same  alkaloid. 

Notes  on  the  Genus  Teucrinm.  .7.  1\[.  Maisch.  (Amer.  Journ. 
Pharni.,  Sept.,  187G.)  Teucrknn  scordiitm,  Lin.,  r/ermnndree  aqnatiqiip 
of  the  French,  Lnclxenhnohlauch.  of  the  Germans,  is  usually  called 


MATERIA    MEDICA.  215 

water  germander  in  English,  because  it  grows  in  moist,  swampy 
meadows,  near  ponds,  etc.  It  is  found  in  western  Asia,  and  through- 
out a  large  portion  of  Europe.  Forty  years  ago  it  was  officinal  in 
most  pharmacopoeias  of  continental  Europe,  but  since  then  has  been 
dismissed  in  the  revised  editions  of  nearly  all,  retaining  a  place  in 
a  few  only. 

The  plant  belongs  to  the  natural  order  of  Lnblahf;,  a  family  oc 
plants  which  is  characterized  by  the  complete  absence  of  deleterious 
properties,  the  active  constituents  found  in  them  being  chiefly  vola- 
tile oil,  associated  in  many  with  more  or  less  of  a  bitter,  non-alka- 
loidal  principle,  and  occasionally  with  a  little  tannin.  The  medical 
prrrperties  of  the  Lnhinhv  are  therefore  mainly  carminative  and  stimu- 
lant, and  frequently  tonic  and  stomachic.  They  are  mostly  in- 
digenous to  the  temperate  regions  of  the  old  world,  the  number 
indigenous  to  the  United  States  being  comparatively  small ;  but 
many  species  have  been  introduced  here  from  Earope,  and  com- 
pletely naturalized  in  some  sections  of  the  United  States. 

The  genus  Tcncrhun  is  classed  with  the  tribe  Ajvjgoidcm,  which 
has  the  upper  lip  short,  or  deeply  notched  and  turned  forward,  so 
as  to  appear  wanting,  the  four  ascending  stamens  projecting  through 
the  slit  in  the  upper  lip.  Several  of  the  European  species  formerly 
enjoyed  a  high  reputation,  among  them  the  one  mentioned,  which, 
together  with  the  allied  species,  T.  scordloules,  Schreb.,  is  regarded 
to  be  the  "SKopBiov  of  Dioscorides.  The  plant  is  softly  pubescent, 
attains  a  hciglit  of  twelve  to  eighteen  inches,  has  sessile,  oblong, 
serrate  leaves,  and  rose-coloured  flowers,  two  or  three  of  which  are 
found  in  the  axils  of  the  leaves.  The  second  species  differs  mainly 
by  being  villous,  and  having  cordately  ovate,  somewhat  clasping, 
leaves.  Both  possess  a  bitter  taste,  and,  in  the  fresh  state,  a  dis- 
tinctly alliaceous  odour.  It  was  formerly  in  repute  as  an  antiseptic 
and  diaphoretic  internal  remedy,  for  gargles,  and  as  a  dressing  for  foul 
ulcers.  "  The  New  London  Dispensatory,"  printed  in  1676,  says 
of  it : — "  It  is  lyptintick,  abstersive,  traumatic,  alexipharmick,  sudo- 
rific, anodyne,  and  pectoral ;  it  opens  obstructions  of  all  the  prin- 
cipal parts,  cleanseth  the  entrails  and  old  ulcers  ;  provokes  urine 
and  the  terms  ;  expectorates  rotten  matter  out  of  the  chest ;  helps 
old  coughs,  asthma,  pleurisies,  inward  ruptures,  biting  and  stinging 
of  serpents  ;  and  potently  resists  poison,  plague,  and  all  pestilential 
diseases.  It  exhilarates  the  heart,  cures  the  bloody  flux,  comforts  the 
stomach,  and  drives  out  the  small-pox  and  measles.  Outwardly,  it 
cleanseth  and  heals  wounds  and  ulcers,  and  cures  pain  of  the  gout. 
The  essence  is  most  effectual  to  the  intentions  aforesaid." 


216  YEAE-BOOK    OF    PHARMACY. 

Similar  but  more  feeble  virtues  were  attributed  to  T.  scorodomia, 
Lin.  (syn.  Scorodina  veteromcdla,  Moench),  likewise  a  European  plant, 
whicli  differs  from  the  former  in  having  petiolate,  cordate-ovate 
leaves,  a  more  distinctly  two-lipped  calyx,  and  yellow  corolla. 

The  fluid  extract  of  water  germander  may  be  made  by  the  U.  S. 
oflBcinal  process  for  fluid  extract  of  chimaphila,  and  may  be  given 
in  doses  of  one-half  to  one  teaspoonful. 

The  following  European  species  were  formerly  employed  medici- 
nally for  their  stimulating  and  tonic  properties,  and  some  still 
enjoy  some  popularity  as  domestic  remedies  in  localities  where  they 
occur: — 

T.  polium,  Lin.,  with  sessile,  linear-lanceolate,  crenate  and  tomen- 
tose  leaves,  and  terminal  white  flowers. 

T.  montanum,  Lin.,  leaves  similar,  with  a  revolute  margin  and 
terminal  yellowish  flowers. 

T.  creticum,  Lin.,  resembling  the  preceding,  but  the  bluish  flowers 
axillary  and  single.  The  closely  allied  T.  rosmarl ni folium,  Lam.,  has 
the  branches  longer  and  more  slender,  and  the  flowers  in  cynules  of 
three  in  the  axils  of  the  bracts. 

T.flavmm,  Lin.,  has  its  greyish  yellow  flowers  similarly  arranged, 
but  the  petiolate  leaves  are  ovate  and  crenate. 

T.  frudicans,  Lin.,  is  the  erha  di  S.  Lorenzo  of  southern  Italy,  and 
has  entire,  oblong  or  oval  sub-coriaceous  leaves,  and  single  axillaiy 
flowers  with  bluish  coi-olla. 

T.  chamcEdnjs,  Lin.,  the  x^MO'^P^^^  of  Discorides;  leaves  short 
petiolate,  ovate  to  obovate,  cuneate  at  base,  crenately  serrate ; 
flowers,  one  to  three,  axillary,  with  purplish  red  corollas. 

T.  hotrys,  Lin.,  leaves  triangular-ovate  in  outline,  pinnatifid  ; 
flowers  axillary,  in  threes  ;  corolla  pale  red,  punctate  in  the  throat. 

These,  and  a  few  other  species,  indigenous  to  southern  Europe 
and  the  basin  of  the  Mediterranean,  most  probably  do  not  differ  in 
their  medicinal  properties  from  Teucrium  Canadense,  Lin.,  the  wood- 
sage  or  germander  of  the  United  States  and  Canada. 

Somewhat  diff'erent  properties  are  met  with  in  T.  inarum,  Lin., 
cat  thyme,  or  Syrian  herb  mastich,  which  is  found  in  the  countries 
bordering  on  the  Mediterranean.  Its  leaves  are  petiolate,  ovate  or 
ovate-oblong,  rather  acute,  white  tomentose  beneath ;  the  rose  red 
flowers  are  single  in  the  axils  of  the  bracts,  and  form  a  terminal 
one-sided  raceme.  It  has  a  strong  aromatic,  somewhat  camphor- 
aceous  odour,  and  an  aromatic,  bitterish  and  acrid  taste.  It  has 
been  employed  internally  in  doses  of  twenty  to  sixty  grains,  in  vari- 
ous spaemodie  and  other  nervous  disorders,  aud  externally  chiefly 


MATERIA    MEDICA.  217 

for  its  errhine  properties.  It  constituted  the  active  ingredient  of  tlie 
Fulvis  sternutatorius  of  some  old  European  ph.armacopceias,  wLicli 
was  composed  of  sweet  marjoram,  3  parts  ;  cat  thyme,  lily  of  the 
valley,  and  orris  root,  of  each  1  part.  Cat  thyme  is  prescribed  in 
Europe  under  the  name  of  Herba  marl  veri. 

Tannin  in  Gentian  Root.  M.  Ville.  {Repert.  de  Phai-m.)  Since 
the  presence  of  tannic  acid  in  gentian  root  asserted  by  Mr.  E.  L. 
Patch  in  a  paper  read  before  the  Massachusetts  College  of  Pharmacy 
has  been  disputed  by  Prof.  Maisch  (see  Year-Booh  of  Pharmacy,  1876, 
228),  the  author  has  been  induced  by  Pi'of.  Leon  Soubeiran  to  re- 
investigate this  subject.  In  the  course  of  his  experiments  with  cold 
infusions  of  the  roots  of  Gentiana  Burseri  and  Gentiana  lutea  he 
obtained  unmistakable  indications  of  the  presence  of  tannin  with 
ferric  chloride,  gelatin,  and  albumen.  He  also  observed  that  in 
decolorizing  the  cold  infusion  with  animal  charcoal  the  colourless 
filtrate  was  free  from  bitterness,  and  ceased  to  give  indications  of 
tannin  with  the  reagents  named.  Further  experiments  were  then 
made  with  the  view  of  ascertaining  whether  the  tannin  found  formed 
part  of  the  colouring  matter  or  of  the  bitter  principle  of  the  root.  The 
I'esultsof  these  experiments  prove  the  absence  of  tannin  in  the  latter, 
but  seem  to  establish  the  tannine;  nature  of  grentianin,  the  colourings 
principle  of  gentian  root.  In  consideration  of  the  chemical  proper- 
ties of  the  colouring  matter,  the  author  suggests  that  gentiania 
should  in  future  be  called  gentiano-tannic  acid.  In  his  opinion 
there  is  much  analogy,  from  a  chemical  point  of  view,  between  gen- 
tianin  and  the  colouring  matter  of  rhatany  root. 

The  Constituents  of  Cotton  Root  Bark.  C.  C.  Drueding.  (Amer. 
Journ.  Pharm.,  1877,  386.)  The  constituents  isolated  by  the  author 
are  a  red  and  a  yellow  resinous  colouring  matter,  a  fatty  oil,  gum, 
glucose,  tannin,  chlorophyll,  and  6  per  cent,  of  mineral  matter. 

Chicle  Gum  and  Monesia  Bark.  J.  R.  Jackson.  (Pharm. 
Jonrti.,  3rd  series,  vii.,  409.)  So  long  ago  as  1839  an  article  was 
published  in  the  Paris  Medical  Gazette  on  a  vegetable  substance 
known  as  monesia.  This  article  was  reprinted  in  the  Pharmaceutical 
Journal,  vol.  iii.  (1843-i4),  p.  292.  It  pointed  out  that  monesia, 
as  then  known,  was  in  the  form  of  hard,  thick  cakes,  covered 
with  yellow  paper,  each  weighing  about  500  grams ;  and  in  this 
form  it  was,  at  the  date  given  above,  a  recent  introduction  into 
France.  The  substance  consisted  of  an  extract  prepared  from 
the  bark  of  the  tree,  the  botanical  source  of  which  was  at  that 
time  unknown,  though  it  was  supposed  to  be  a  species  of  Chry- 
soplijjllnm.     It   was  known,  however,   to   travellers   as   goharem  or 


218  YEAH-BOOK    OF    PnARMACY. 

hnranhcm.  The  bark  was  described  as  smooth  and  grejish,  in 
appearance  bke  that  of  the  plane  tree,  but  much  thicker,  show- 
ing' an  imbricated  fracture  and  having  a  sweet  taste.  The  extract 
wag  in  colour  a  deep  brown,  very  friable,  and  when  broken 
having  the  appearance  of  a  well  roasted  cocoa-nnt ;  entirely  soluble 
in  water  ;  at  first  sweetish  to  the  taste,  like  liquorice,  but  after- 
wards becoming  astringent,  leaving  a  well  marked  and  lasting 
acid  taste  in  the  mouth,  which  is  particularly  felt  in  the  tonsils. 
The  ailments  in  which  monesia  was  administered  were  diarrhoea, 
leucorrhoea,  uterine  hemorrhage,  inflammation  of  the  mucous  mem- 
brane, etc.  Such  is  a  brief  re.«7ni?e  of  what  has  been  already  pub- 
lished on  monesia,  which  will  be  found  in  detail  at  the  reference 
given  above,  as  well  as  at  pp.  125,  187,  vol.  iv.  (1844-45),  of  the 
PharmaceuiicalJournal,  the  latter  being  a  quotation  from  the"  Sys- 
tema  Materia?  !Medic£e  Vegetabilis  Braziliensis."  In  this  the  plant 
is  referred  to  as  the  Chn/sopJujIlum  hiranhnn  of  Riedel. 

Quite  recently  the  plant  has  been  brought  to  notice  again,  as 
"  chicle,"  in  New  York,  whence  it  is  imported  from  Mexico  for 
manufacturing  purposes,  such  as  mixing  with  rubber  for  insulating 
telegraph  cables.  Some  experiments  have  also  been  made  with  it 
with  a  view  of  manufacturing  a  paint  for  the  bottoms  of  vessels; 
beside  which  an  essential  oil,  adapted  for  perfumery  purposes  can, 
it  is  said,  be  extracted  from  it.  A  specimen  of  this  chicle  gum  has 
recently  been  received  at  the  Kew  Museum.  In  appearance  it  is 
somewhat  like  crude  gutta-percha,  but  more  friable  or  brittle.  It 
it  easily  made  plastic  in  warm  water ;  but  from  experiments  made 
in  this  country  it  does  not  seem  .suitable  for  mixing  with  india- 
rubber  for  telegraphic  purposes,  as  it  makes  the  rubber  itsilf  more 
brittle.  Besides  the  name  of  chicle,  the  substance  seems  to  be 
known  in  the  New  York  market  as  "  jNIexican  gum  "  and  "rubber 
juice."  The  identification  of  this  gum  with  the  plant  yielding 
monesia  is  founded  as  yet  only  on  the  fact  that  the  plant  yielding 
the  former  is  known  as  zapota  or  zapote,  and  is  described  as  a 
saponaceous  tree;  and  further,  that  it  yields  a  medicinal  product 
known  as  monesia.  Specimens  of  the  plant  itself  have  not  yet  been 
received;  therefore,  though  all  the  circumstances  indicate  them  to 
be  one  and  the  same  thing,  it  cannot  be  decided  as  a  certainty  until 
the  reception  of  actual  specimens  yielding  chicle  gum. 

With  regard  to  the  curanhem  or  guaranhem  of  Brazil,  which  is 
also  known  as  the  imiracem,  mohica,  and  cusca  doce  (sweet  bark), 
it  is  conclusive  that  the  plant  furnishing  them  is  the  Chry.^oplujUum 
(jhjcophJocum,  Gazar.  (C.  buranhem,  Riedel).     It  is  one  of  the  com- 


MATERIA    JIF.DICA.  2  19 

monest  trees  in  Brazil,  and  is  met  "with  even  in  the  environs  of  TJio 
de  Janeiro,  where  Cazareth  studied  it  (on  the  Corcavado),  as  vreU  as 
Telloso  and  Peckholt  in  Cantagallo.  Both  in  tlie  provinces  of  the 
north  as  well  as  in  the  Antilles,  it  is  well  known  and  employed  in 
Tnedicine  and  in  veterinary  practice.  The  ])ark  is  carried  to  market 
in  fragments  of  from  two  to  throe  millimetres  thick,  and  five  to 
twenty  centimetres  in  length.  It  is  of  red  or  brownish  colour, 
according  to  the  season  iu  wdiich  it  is  gathered,  and  according  to 
the  age  of  the  plant.  When  recently  collected,  the  hark  is  abund- 
antly milky,  and  has  a  strong  astringent  and  sweetish  taste. 

Monesia  as  now  met  with  presents  under  the  form  of  transparent 
plates  of  a  yellowish  white  colour  a  substance  easily  pulverized. 
When  reduced  to  powder  it  has  a  white  colour.  It  is  soluble  iu 
alcohol  and  in  water,  but  barely  so  in  sulphuric  acid.  When  put  into 
water  and  shaken  it  produces  a  froth  like  soap-suds.  In  Brazil  the 
preparations  of  the  bark  of  this  plant  are  used  both  internally  and 
externally.  It  is  considered  an  excellent  astringent,  applied  in  the 
same  cases  as  the  ratanhia.  Iu  Bahia,  Leigipe,  and  sundry  other 
provinces,  it  is  the  usual  medicine  for  cases  where  an  energetic 
astringent  is  required.  The  preparations  employed  are,  the  decoc- 
tions for  baths  and  clysters;  the  extract  for  pills  and  to  put  on 
cataplasms  ;  and  the  syrup  or  wine.  The  disorders  in  which  this 
medicine  is  most  efficacious  are  diarrhoea,  intermittent  fevers, 
dysentery,  hemorrhage,  ulcerations  of  the  gastro-intestinal  canal, 
quinsy,  etc. 

With  regard  to  the  physiological  action  of  monesia.,  it  is  said  that, 
notwithstanding  its  sweetish  taste,  it  belongs  strictly  to  the  astrin- 
gents and  tonics.  Its  astringency  becomes  less  sensible  by  the  pre- 
sence of  the  saccharine  principle  contained  in  the  bark.  On  ulcers 
it  produces  a  sensation  of  pain,  accompanied  with  great  heat,  which 
lasts  for  hours,  and  sometimes  even  for  days,  afterwards  accom- 
panied with  a  rapid  formation  of  numerous  fleshy  pimples.  On  the 
fibres  of  the  uterus  it  acts  with  the  same  effect  as  ergot  of  rye. 

^[onesine,  the  acrid  principle,  is  applied  in  doses  of  1  to  3  decigrams. 
The  syrup  has  a  great  reputation  against  haemoptysis,  the  extract 
in  ulcerations  of  the  mouth  and  the  gastro-intestinal  canal,  as 
has  already  been  said.  Externally  the  extract,  either  with  gly- 
cerin or  pure,  is  considered  very  efficacious  for  wounded  breasts, 
lips,  and  arms;  the  powder  is  also  used  for  similar  purposes. 
With  regard  to  the  industrial  applications  of  the  bark  of  Lucuma 
ijlycyjihlcciim,  it  is,  on  account  of  its  astringency,  used  both  for  tan- 
ning leather  and  for  dyeing  purposes;  further  than  this,  it  is  said  to 


220  YEAR-BOOK    OF   PHARMACY. 

coutain  a  quantity  of  saponaceous  matter  which  might  be  employed 
for  cleaning,  but  which  does  not  seem  capable  of  development  to 
any  extent  so  as  to  make  it  commercially  profitable. 

The  foregoing  remarks  on  the  products  of  Lacuma  ghjcyphlceum, 
or  monesia,  are  abstracted  from  a  report  recently  drawn  up  for  the 
Brazilian  G-overnment  by  some  of  the  best  authorities  on  the  subject. 
Although  monesia  is  not  now  used  in  Brazil  so  much  as  formerly, 
it  still  has  a  reputation. 

Examination  of  the  Rhizome  of  Iris  Versicolor.  C.  H.  Mar- 
quardt.  (Abstract  from  an  inaugural  essay:  Amer.  Journ.  Fharm., 
1876,  406.) 

Eight  troy  ounces  of  the  rhizome,  in  moderately  fine  powder,  was 
exhausted  by  alcohol,  sp.  gr.  'SST),  and  the  alcohol  distilled  off. 
The  residue  had  a  very  acrid  taste,  and  separated  into  an  upper, 
dark  brown,  perfectly  transparent  layer,  and  a  lower  one  of  a  more 
yellowish  colour;  the  former  was  soluble  in  alcohol,  petroleum 
benzine,  chloroform,  and  ether;  the  latter  dissolved  completely  in 
alcohol,  partly  in  ether,  and  not  in  chloroform  or  benzine.  The 
entire  residue  was  exhausted  with  the  ether,  and  the  solvent  evapo- 
rated, leaving  a  dark  brown  oleo-resin,  of  a  slightly  disagreeable 
odour  and  a  very  acrid,  persistent  taste.  Ammonia  water  dissolved 
a  small  portion  of  it,  but  effected  no  separation.  Treated  with  cold 
solution  of  potash,  a  yellowish  white  emulsion  was  formed,  from 
which  an  oily  liquid  separated,  which  was  purified  by  dissolving  in 
ether,  and  had  then  a  light  colour  and  a  pleasant  bland  taste,  which 
after  awhile  became  acrid. 

The  potash  solution  was  carefully  neutralized  with  sulphuric  acid, 
concentrated  by  evaporation,  and  treated  with  ether,  which  dissolved 
a  brown,  soft  resin,  possessing  the  acrid  taste  in  a  very  marked 
degree,  and  yielding  with  nitric  acid  a  beautiful  purple  coloured 
mass,  becoming  yellow  and  tough  after  some  hours. 

The  residue  left  by  treating  the  alcoholic  extract  with  ether  was 
of  a  yellow  colour,  had  a  sweet  taste,  was  soluble  in  water  and 
alcohol,  and  by  Trommer's  test  proved  to  be  glucose. 

The  dregs,  exhausted  by  alcohol,  were  extracted  with  diluted 
alcohol,  sp.  gr.  '941 ;  the  light  yellow  tincture  was  evaporated  to  a 
syrupy  consistence  and  set  aside  for  a  week,  when  a  sweet,  solid 
mass  remained.  Its  solution  in  water  was  precipitated  by  subacetate 
of  lead,  and  after  removing  the  excess  of  lead  by  sulphuretted 
hydrogen,  Trommer's  test  indicated  in  the  filtrate  the  presence  of 
glucose. 

The  precipitate  on   being  suspended  in  warm  water  and  treated 


I 


MATERIA    MKDICA.  221 

■with  snlpHuretted  hydrogen,  yielded,  on  evaporating  tLo  water,  a 
yellow  viasf!,  having  a  peculiar,  not  unpleasant,  bitter  taste. 

The  exhausted  powder  yielded  to  cold  water  some  albumen,  separ- 
able by  heat,  and.  gummy  matter,  precipitated  by  alcohol,  and  the 
solution  of  which  formed  a  jelly  with  ferric  chloride.  Hot  water 
dissolved  mainly  starch  from  the  exhausted  powder. 

On  distilling  the  fresh  rhizome  with  water,  an  opalescent  dis- 
tillate, of  a  peculiar  odour,  was  obtained,  from  which  a  white  cam- 
2)horaceous  substance  separated,  scaly  in  appearance,  of  a  faint 
odour,  nearly  tasteless,  and  soluble  in  alcohol. 

The  Detection  of  Admixtures  in  Colocynth  Powder.  Wm.  J. 
Clark.  (Abstract  of  a  paper  read  before  the  North  British  Branch 
of  the  Pharmaceutical  Society,  Dec.  13th,  1876.)  The  microscope 
affords  a  ready  means  for  the  recognition  of  an  admixture  of  seed 
or  rind  with  the  true  pulp  of  colocynth.  The  most  general  and 
characteristic  test  for  the  former  is  to  be  found  in  the  cells  of  the 
cotyledons.  If  a  small  portion  of  the  suspected  powder  be  placed 
on  a  glass  slip,  a  drop  of  water  added,  and  the  cover  glass  gently 
rubbed  on  it,  so  as  to  extend  the  drop,  these  granules  will  be  readily 
noticed.  In  the  true  powder  no  granules  are  to  be  seen,  or  at  the 
most  but  one  or  two,  but  in  proportion  as  more  or  less  seed  is  pre- 
sent, so  are  the  granules  more  or  less  numerous.  Unless  these  con- 
stitute a  considerable  bulk  of  the  powder,  their  presence  should  only 
be  considered  accidental,  and  the  powder  not  be  condemned  on  this 
account.  It  will  be  evident  that  when  the  seed  is  powdered  the 
tissues  will  be  also  broken  up,  and  fragments  of  these  may  be 
noticed.  The  commonest  and  most  easy  of  detection  is  the  double 
walled  sac  enveloping  the  embryo,  showing  on  the  outer  side  elon- 
gated, more  or  less  hexagonal  cells,  and  in  the  inner  side  a  charac- 
teristic structure  shown  in  the  woodcut.  (See  Pliarm.  Jouru., 
p.  509.)  Besides  this,  the  spiral  vessels  are  sometimes  present, 
but  these  cannot  be  with  certainty  distinguished  from  those  of  the 
pulp.  Stomata  may  and  do  occur,  but  their  presence  is  so  difficult 
of  detection  that  they  cannot  be  depended  on.  The  episperm  again, 
although,  it  shows  a  characteristic  structure  on  section,  yet,  in  the 
state  of  powder,  cannot  be  recognised.  The  rind,  on  the  other 
hand,  is  still  less  frequently  met  with,  but  the  characteristic  stomata, 
in  this  case  easily  seen,  would  furnish  a  ready  means  of  detection. 
In  none  of  the  examples  examined  by  the  author  was  any  rind  de- 
tected. Besides  the  admixture  of  the  seed,  powdered  colocynth  is 
liable  to  contain  starch  as  an  adulterant,  but  this  of  course  is  readily 
detected  both  by  iodine  and  a  microscope. 


222  YEAK-BOOK    OF    i'HAUMACY. 

The  author's  lepurt  in  the  I'liarmaceatlcal  Juurual  is  illastrateJ 
by  au  excellent  ^Yoodcut,  showiug  the  microscopic  appearance  under 
u  power  of  470  diameters  of  the  inner  layer  of  embryo  sac,  the 
outer  layer  of  ditto,  cells  of  palisaded  layer  with  granules,  stomata 
from  cotyledon,  granules  from  cotyledons,  epidermis  of  rind,  aud 
starch  granule. 

Pitliry.  Baron  Mueller.  (British  MedicalJournal.)  Aprevious 
notice  of  this  drug  will  be  found  in  the  Year-Boole  of  JPJiannacy, 
1874,  62.  Baron  Mueller  gives  in  an  Australian  journal  an  account 
of  his  recent  examination  of  the  leaves  of  the  "  pitury,"  said  to  be  of 
great  power  as  a  stimulant,  and  to  be  found  growing  in  desert  scrubs 
from  the  Darling  River  and  Barcooto  to  West  Australia.  It 
is  his  opinion  that  it  is  derived  from  Duboisii  Hojnvoodii,  described 
by  him  in  1861,  the  leaves  of  which  are  chewed  by  natives  of  Central 
Australia  to  invigorate  themselves  during  long  foot-journeys.  The 
blacks  use  it  to  excite  their  courage  in  warfare ;  a  large  dose  infuri- 
ates them.  The  Sidney  Herald  is  informed  also  that  some  dry 
leaves  and  stems,  said  to  come  from  far  beyond  the  Barcoo  country, 
aud  called  "  pitcherine,"  are  used  by  the  aborigines  as  "we  use 
tobacco,  for  both  chewing  and  smoking  ;  and  it  is  stated  also  that  a 
small  quantity  causes  agreeable  exhilaration,  prolonged  use  result- 
iug  in  intense  excitement.  It  is  observed,  that  the  blacks,  after 
chewing  the  lea;ves,  plaster  the  quid  so  formed  behind  the  ears, 
believing  that  this  increases  its  eS'ect. 

The  Root  of  Euphorbia  Ipecacuanha.  P.  H.  Dilg.  (Amer.  Journ. 
Pharm.,  Nov.,  1870.)  The  author  collected  the  root  in  New  Jersey 
late  in  September,  and  on  repeating  some  of  Mr.  Petzelt's  experi- 
ments (see  Year-Booh  uf  Bhanuacy,  1874,  125)  did  not  obtain  any 
reaction  for  glucose  until  after  the  decoction  had  been  boiled  with 
an  acid. 

The  alcoholic  extract  obtained  by  spontaneous  evaporation  was  of 
a  light  brown  colour,  and  contained  some  crystals  ;  ether  extracted 
from  it  some  oil  and  waxy  matter,  and  a  compound,  which,  on 
evaporation  from  petroleum  benzine,  yielded  clusters  of  radiating 
crystals. 

On  percolating  the  root  with  petroleum  benzine  and  evaporating 
the  menstruum,  a  yellow  tenacious  mass,  intermingled  with  thin 
colourless  needles,  was  obtained.  This  benzine  extract  was  com- 
pletely dissolved  by  chloroform  and  bisulphide  of  carbon,  the  latter 
solution  being  turbid ;  ether  dissolved  it  partially,  leaving  a  white 
flaky  residue,  and  alcohol  acquired  a  yellow  colour  without  affect- 
ing the  shape  of  the  extract,  which  appears  to  consist  mainly  of 


I 


MATERIA    MEDICA.  223 

caoutclione.  From  tlie  alcoliolic  solution  a  wartj  crystalline  mass 
was  obtained,  which  responded  to  the  test  for  euphorbon  as  given 
by  Fliickiger  ("Pharmacogi-aphia,"  p.  504). 

The  author  did  not  succeed  in  isolating  the  emetic  principle;  and 
in  concluding  his  essay  he  states  that  only  two  houses  in  this  city 
quote  Eaphorhla  ijjesacuanha  in  their  price  lists,  but  one  onlv  had 
it  in  stock,  chai'ging  for  it  75  cents  per  pound.  On  examining  a 
dozen  price  lists  from  eclectic  druggists  in  diSei-ent  parts  of  the 
country,  one  from  Boston  was  the  only  one  quoting  it,  and  fi-om 
that  house  a  package  was  obtained,  marked  Euphorbia  A)uericana, 
but  containing  the  root  of  Gillenla  stipulacea.  If  it  was  ever  used 
to  any  extent,  the  drug  has  evidently  become  obsolete,  and  might 
well  be  dropped  from  the  Pharmacopoeia. 

Potalia  Amara.  A.  Halle  r  and  E.  Meckel.  (Juuru.  de  Phanu.  et 
de  Cktin.,  xxiv.  247.)  The  authors  have  received  and  examined  a 
few  fruit-bearing  specimens  of  this  plant,  which  is  a  native  of  Cayenne. 
Aublet,  who  has  given  a  short  description  of  it  in  his  "Histoire  de  la 
Guyane  Fran^aise,"  ii.,  394,  says:  "All  parts  of  the  plant  are  bittei-. 
The  young  stems  exude  a  yellow,  granular,  transparent  resin,  which 
when  burnt  emits  an  odour  resembling  that  of  benzoin.  Infusions 
of  the  leaves  and  of  wood  of  young  stems  are  employed  in  small 
doses  as  a  remedy  for  syphilis;  in  larger  doses  they  act  as  emetics." 

The  statement  that  all  parts  of  the  plant  have  a  bitter  taste  is  con- 
tradicted by  the  authors,  who  found  that  the  leaves,  bark,  and  root, 
are  devoid  of  bitterness ;  whereas  the  wood  is  both  aromatic  and 
bitter. 

As  potalia  belongs  to  the  Strychnece,  various  parts  of  the  plant 
were  examined  for  strychnine  and  brucine,  but  no  satisfactory  evi- 
dence of  their  presence  could  be  obtained.  The  authors  intend  to 
resume  their  investigation  on  the  receipt  of  larger  quantities  of 
material.  The  results  thus  far  obtained  point  to  the  presence  of  a 
bitter  poisonous  principle  possessing  powerful  emetic  properties. 

Hoang-Nan.  M.  Planchon.  (Joum.  de  Pharm.  et  de  Ghlm., 
1877,  384.)  Hoang-Nan  is  the  name  of  a  bark  which  is  said  to  be 
much  esteemed  in  Tong-King  (in  Eastern  Asia)  as  a  remedy  fur 
hydrophobia.  Specimens  of  it  received  by  the  author  correspond  in 
every  particular  with  the  bark  of  Strychnos  nux  vomica.  Missionaries 
report  that  the  brow^nish  dust  which  covers  the  bark  is  the  part  em- 
ployed by  the  natives,  who  regard  the  woody  portion  of  the  bark  as 
inert,  but  believe  the  external  dust  to  contain  a  strong  poison.  From 
Pelletier's  investigation  of  false  angostura  bark,  it  is  known,  how- 
ever, that  the  poisonous  constituents  (strychnine  and  brucine)  are 


224  YEA.E-BOOK    OF    PHARMACY. 

located,  not   iu    tlie    outer    corky  layer,   but   in   the  woody  tissue 
below. 

Some  Constituents  of  Gelsemium  Sempervirens.  F.  L.  Sonnen- 
schein.  (Pharm.  Journ.,  from  Ber.  der  deufsch.  Ghem.-Ges.,  xi., 
1182.)  For  several  years  past  various  preparations  of  the  so-called 
Carolina  jasmine  {Gelsemium  sempervirens,  Pers.)  have  been  usxl 
in  medicine  in  North  America,  the  two  principal  being  the  fluid 
extract  and  "gelseniin."  The  first  of  these  is  a  concentrated  alco- 
holic extract,  the  latter  is  a  dried  alcoholic  ethereal  extract,  contain- 
ing much  resin.  Notwithstanding  that  different  chemists,  and  more 
recently  Wormley,  have  been  engaged  iu  the  investigation  of  this 
drug,  hitherto  no  exact  information  has  been  given  as  to  the  com- 
position and  nature  of  the  two  principal  constituents,  namely,  a 
non-nitrogenous  body  approaching  to  an  acid,  and  a  non-nitro- 
genous basic  compound.  In  a  paper  lately  read  before  the  Berlin 
Chemical  Society,  Professor  Sonnenschein  gives  the  following  in- 
formation, which  is  based  upon  a  series  of  experiments  carried  out 
in  his  laboratory  with  a  suitable  supply  of  material,  by  Mr.  C. 
Robbins,  of  New  Tork. 

The  powdered  root  was  extracted  to  exhaustion  with  a  mixture  of 
equal  parts  of  alcohol  and  water  ;  the  extract  was  concentrated,  and 
after  separation  of  the  resin  thus  thrown  out  of  solution  basic  lead 
acetate  was  added,  as  long  as  any  precipitate  was  formed.  This 
precipitate  served  especially  for  the  preparation  of  the  indifferent 
compound.  A  mixture  of  one  part  of  ether  and  three  parts  of 
alcohol  used  instead  of  the  aqueous  alcohol  for  extraction  gave  a 
larger  yield.  The  filtered  liquid  was  used  for  the  separation  of  the 
nitrogenous  body. 

The  lead  precipitate  was  suspended  in  water,  decomposed  by  sul- 
phuretted hydrogen,  filtered,  the  filtrate  concentrated  by  evapora- 
tion, and  the  liquid  so  obtained  was  shaken  several  times  with  ether. 
The  ethereal  solution,  upon  spontaneous  evaporation,  left  behind 
some  light  acicular  crystals,  which  had  to  be  separated  from  adher- 
ing resinous  matter  by  treatment  with  absolute  alcohol.  The  same 
compound  may  be  obtained  direct  by  shaking  the  commercial  fluid 
extract  with  ether,  a  method  that  was  adopted  by  Wormley. 

Thus  purified,  this  substance  is  white,  crystallizes  readily  in  tufts, 
is  without  smell,  and  almost  tasteless,  and  possesses  feebly  acid  pro- 
perties. The  acicular  crystals  are  best  obtained  after  slow  crystal- 
lization from  an  alcoholic-ethereal  solution.  If  heated  to  about 
1G0°  C,  this  substance  melts,  and  solidifies  upon  cooling  to  an  amor- 
phous mass.     Upon  heating  it  above  the  melting-point  it  is  decom- 


MATERIA    MEDICA. 


225 


posed  and  turns  brown,  and  upon  raising  the  temperature  still 
higher,  it  is  at  last  completely  volatilized.  If  heated  very  carefully, 
a  portion  can  be  sublimed.  The  compound  is  soluble  with  difficulty 
in  cold,  but  much  more  readily  in  hot  water ;  it  is  soluble  in  about 
100  parts  of  cold  alcohol,  almost  insoluble  in  pure  ether,  but  easily 
soluble  in  ether  containing  alcohol. 

The  aqueous  solution  is  distinguished  by  its  fluorescence,  which  can 
be  observed  even  after  very  considerable  dilution.  In  an  alkaliue 
solution  this  appearance  becomes  yet  more  manifest ;  the  solution 
then  appears  yellow  by  transmitted  light,  and  by  reflected  light  blue. 

Concentrated  sulphuric  acid  dissolves  this  substance  mth  a  red- 
dish yellow  colour ;  carefully  heated,  the  solution  becomes  chocolate 
browTi.  Hydrochloric  acid  causes  no  particular  change  of  colour. 
If  the  substance  be  shaken  with  a  small  quantity  of  nitric  acid  a 
yellow  solution  results,  which  upon  the  addition  of  ammonia  takes 
a  deep  blood  red  colour.  This  reaction  is  so  delicate  that  0'00002 
gram  can  be  detected  by  it. 

The  same  results  were  obtained  by  Wormley,  who  named  the  com- 
pound "  gelseminic  acid  ;  "  principally  because  of  its  acid  reaction, 
but  also  because  the  compound  with  an  alkali  produces  precipitates 
in  the  solutions  of  most  of  the  heavy  metals.  These  precipitates 
Wormley  considered  to  be  insoluble  gelseminates.  Careful  experi- 
ments and  examination  under  the  microscope  have,  however,  proved 
that  with  the  exception  of  the  lead  compound  they  consisted  of  the 
hydrated  oxides  of  the  metals  mixed  ^ath  the  supposed  acid. 

It  was,  therefore,  thought  probable  that  this  substance  instead  of 
being  a  new  acid  would  prove  to  be  identical  with  assculin  (formerly 
called  polychrom),  obtained  from  the  bark  ^sculus  Hippocastanum. 
An  agreement  was  observed  in  its  external  characters  as  well  as  its 
chemical  behaviour,  especially  in  the  blue  fluorescence  of  the  aqueous 
solution,  the  dichroism  of  an  alkaline  solution,  the  reaction  with 
nitric  acid  and  ammonia,  and  its  behaviour  at  high  temperatures. 
This  agreement  was  established  by  pf^rallel  experiments  with  com- 
mercial aesculin.  Also,  by  digestion  of  sesculin  prepared  from  gel- 
semium  with  dilute  sulphuric  acid  sugar  and  separated  and  detected 
by  Fehling's  test. 

In  order  further  to  establish  the  identity  of  the  two  substances  a 
combustion  was  made  with  some  of  the  prepared  substance  that 
had  been  dried  at  115°  until  it  ceased  to  lose   weight.     There   was 

found — 

I.  II. 

C 52-04  51-82 

H 5-18  4-98 

Q 


22G  YEAR-BOOK    OP    PHARMACY. 

According  to  Rochleder,  sescalin  has  the  formula  C30  Hg^  O^g,  which 
would  give  a  percentage  composition  of  C,  51'57  ;  H,  4" 8 7. 

A  further  confirmation  was  found  in  the  hydration.  The  air- 
dried  substance  obtained  from  gelsemium  lost  at  110°  C.  473  per 
cent  of  water,  -^sculin  =  Cg^  E.^  0^^  +  2  aq.  lost  by  drying  4-90 
per  cent. 

Professor  Sonnenschein,  therefore,  thinks  there  can  be  no  doubt 
that  the  acid  reacting  body  prepared  from  gelsemium  is  perfectly 
identical  with  sesculin. 

The  solution  from  which  the  lead  precipitate  bad  been  sepai^ated 
was  freed  from  dissolved  lead  by  sulphuretted  hydrogen ;  then  from 
the  still  acid  liquid  any  yet  remaining  aesculin  was  removed  by  shak- 
ing with  ether,  the  ether  was  chased  off  by  heat,  and  potash  added 
up  to  an  alkaline  reaction.  A  light  flocculent  precipitate  was  thus 
thrown  down,  which  was  collected  on  a  filter,  and  after  washing, 
which  could  not  be  continued  long  on  account  of  it  being  slightly 
soluble,  it  was  dissolved  for  purification  in  hydrochloric  acid.  The 
filtered  solution  was,  after  the  addition  of  potash,  several  times 
shaken  with  ether,  which  was  left  to  evaporate  spontaneously,  when 
a  colourless,  transparent,  varnish -like  coating  was  left  on  the  sides 
of  the  vessel.  It  was  found  that  the  largest  yield  of  this  substance 
was  obtained  from  the  aqueous  alcoholic  extract. 

When  the  dish  was  gently  warmed  the  residue  puffed  up  strongly 
whilst  parting  with  entangled  ether,  and  then  appeared  as  an 
amorphous,  transparent,  brittle  mass,  which  could  be  rubbed  to  an 
almost  colourless,  perfectly  amorphous  powder.  Upon  gently  heat- 
ing this  it  melted,  under  100°  C,  to  a  colourless  liquid  ;  at  a  higher 
temperature  it  was  partially  decomposed.  In  water  it  was  with 
difficulty  soluble,  more  readily  in  alcohol,  and  very  freely  in  ether 
and  chloroform.  Its  reaction  was  strongly  alkaline,  and  its  taste 
very  bitter. 

The  behaviour  of  this  body,  which  has  all  the  characters  of  an 
alkaloid,  and  has  been  named  gelsemine,  was  briefly  as  follows : — 

It  completely  neutralized  acids,  but  hitherto  no  crystallizable  salts 
have  been  prepared.  The  combination  with  hydrochloric  acid,  upon 
evaporation  over  sulphuric  acid,  leaves  an  amorphous  mass,  which  is 
white  in  the  centre,  red  towards  the  periphery,  and  bkie-grey  at  the 
outer  edge. 

The  residue  readily  formed  a  solution  with  water,  which  only 
when  concentrated  gave  a  white  precipitate  with  tannin,  but  when 
diluted  gave  it  first  with  ammonia.  Gold  chloride  gave  a  yellow 
precipitate  that  was  not  altered  by  heating.     Iodine  in  iodide  of 


MATERIA    MEDICA.  227 

potassium  gave  a  flocculent  red-brown  turbidity,  wbicli  became 
somewhat  conglomerated  by  beating.  Potassio-mercuric  iodide 
gave  a  white  flocculent  precipitate,  which  dissolved  upon  heating, 
and  again  separated  on  cooling.  Phosphomolybdic  acid  gave  a 
flocculent  yellow  precipitate.  Platinic  chloride  gave  an  amorphous 
citron  yellow  precipitate,  soluble  in  water,  especially  upon  heating. 
It  was  also  readily  soluble  in  alcohol.  An  aqueous  solution  of  the 
platinum  salt  left  upon  spontaneous  evapoi*ation  transparent  square 
octahedra,  which  upon  the  addition  of  water  immediately  took  the 
amorphous  form,  with  separation  of  platinum  chloride. 

The  pure  alkaloid  dissolves  in  concentrated  nitric  acid  with  a 
yellow- green  colour.  In  concentrated  sulphuric  acid  it  gives  at 
first  the  same  colour,  but  this  passes  immediately  to  a  reddish 
brown,  and  upon  heating  to  a  dark  dirty  red  coloui*. 

If  gelsemine  be  dissolved  in  concentrated  sulphuric  acid  and 
potassium  bichromate  be  added,  it  takes,  especially  at  the  line  of 
contact,  a  cherry  red  colour,  changing  a  little  to  violet,  which  soon 
forms  a  bluish  green  spot.  This  reaction  cannot  be  confounded 
with  that  of  strychnine,  although  it  shows  some  similarity.  If 
instead  of  potassium  bichromate  ceroso-ceric  oxide  be  added  to  the 
sulphuric  acid  solution  there  is  produced  a  bright  light  cherry  red 
colour,  especially  at  the  point  of  contact,  which  by  stirring  is  dif- 
fused through  the  mass.  This  reaction  takes  place  so  sharply  with 
the  smallest  trace  that  it  may  be  looked  upon  as  the  best  test  for 
the  presence  of  gelsemine. 

The  amorphous  platinum  precipitate  left  upon  incineration  16'25 
and  16'85  per  cent,  of  metallic  platinum.  The  hydrochloric  acid 
compound  contained  8"  73  per  cent,  of  chlorine.  Upon  incineration 
with  soda  lime  the  nitrogen  in  two  experiments  was  found  to  equal 
7"26  and  7"23  per  cent.  The  carbon  found  in  two  experiments  was 
66-10  and  66"41  per  cent.,  and  the  hydrogen  9"44  and  10"05.  This 
allows  of  the  construction  of  the  following  formula  for  gelsemine — 
CnHigNOg. 

Calculated.  Found. 


I. 

II. 

C  11  =  132 

67-00 

66-41  . 

,  66-10 

H19=  19 

9-64 

10-05  , 

,   9-44 

N   =  14 

7-10 

7-26  . 

7-23 

02  =  32 

16-24 

16-28  . 

17-23 

This  formula,  however,  has  to  be  doubled  if  it  depends  on  the 
hydrochloric  acid  compound,  since  this  contains  8-73  per  cent,  of 
chlorine.     {0^  H^g  N  03)2  +  H  CI  requires  8-24  per  cent  of  chlorine. 


228 


YEAR-BOOK   OF    PHARMACY. 


According  to  the  platinum  left  after  incineration  the  platinum 
compound  must  have  a  composition  represented  by  [(Cj^  H^gNOo)^ 
H  CI]  Pt  Cl^,  which  would  explain  its  behaviour  in  water  by  the 
formation  of  a  basic  salt. 

0"012  gram  of  the  hydrochloric  acid  compound  injected  into  the 
leg  of  a  strong  pigeon  caused  manifestations  of  cramp,  followed  by 
death  in  thirty-six  minutes.   Similar  results  were  obtained  with  frogs. 

The  Relative  Value  of  ColcMcimi  Root.  Prof.  Beckert.  (From 
an  inaugural  essay:  Amer.  Journ.  Pharm.,  1877,  433.)  This  sub- 
ject was  suggested  by  several  pharmacists,  who  of  late  have  found 
it  a  difficult  matter  to  obtain  colchicum  root  which  on  breakinsr 
presented  a  clear  white  colour.  The  article,  as  obtained  from  the 
wholesale  druggists,  consisted  of  tubers  which  had  been  sliced  very 
irregularly.  Out  of  a  pound  lot  not  less  than  seven  whole  tubers 
were  taken,  the  remainder  varying  from  one-sixth  to  one-half  inch 
in  thickness.  These  pieces,  when  broken,  presented  quite  a  varied 
appearance,  their  colour  being  all  shades  between  white  and  black  ; 
and  it  was  noticed  that  the  lighter  coloured  roots  were  mostly  easy 
to  break,  and  many  of  them  of  a  mealy  character,  whereas  the  darker 
ones  were  diflBcult  to  break,  and  had  a  somewhat  resinous  appear- 
ance. A  quantity  of  the  root  was  broken  piece  by  piece,  and  then 
separated  into  three  grades,  according  to  colour,  white,  slate-coloured, 
and  brown  or  blackish,  particular  care  being  taken  in  the  sorting. 
Upon  weighing,  it  was  found  that  the  white  root  constituted  only 
one-sixth,  while  the  gi'ey  root  comprised  not  quite  two-sixths,  and 
the  black  root  a  little  over  three-sixths  of  the  article  examined. 
These  results  also  agree  with  the  observations  of  several  resident 
pharmacists. 

The  methods  used  to  determine  were  as  follows  : — Two  troy  ounces 
of  each  of  the  three  grades  of  roots  Avere  exhausted  by  means  of 
alcohol,  yielding  in  each  case  about  twelve  fluid  ounces  of  tincture ; 
these  tinctures  varied  in  colour  according  to  the  grade  of  root  used, 
that  from  the  white  root  being  lightest.  This  indicates  the  solu- 
bility in  the  alcohol  of  the  foreign  colouring  matter  present  in  the 
grey  and  black  roots.  In  preparing  these  tinctures,  care  was  taken 
to  percolate  them  under  as  similar  circumstances  as  possible. 

The  tinctures  obtained  were  separately  evaporated  by  means  of  a 
water  bath,  the  residue  was  treated  with  distilled  water,  and  poured 
upon  a  filter,  in  order  to  separate  resinous  matter ;  the  filtrate  was 
washed  with  slightly  acidulated  water  until  each  filtrate  measured 
100  c.c.  Dilute  sulphuric  acid  was  used  for  acidulating  the  solu- 
tions, which  were  volumetiically  tested  with  Mayer's  solution,  in 


MATERIA    MEDICA. 


229 


qaantities  varying  from  5  to  15  c.c.  In  the  preliminary  experiments 
the  solutions  were  variously  diluted,  and  it  was  observed  that  the 
results  were  very  considerably  influenced  thereby,  an  observation 
previously  made  by  Dragendorff.  To  serve  as  a  basis  for  compari- 
son, the  experiments  were  afterwards  made  with  solutions  of  uni- 
form strength,  as  stated  above,  partly  without  any  other  addition, 
and  partly  as  recommended  by  Dragendorff,  after  the  addition  of 
a  concentrated  solution  of  chloride  of  sodium,  to  increase  the  dis- 
tinctness of  the  reaction.  The  three  grades  of  the  root  required  for 
1  c.c.  respectively  "O-IOS,  •0414,  and  "0462  of  Mayer's  solution. 

Five  troy  ounces  of  each  of  the  roots  were  next  exhausted  by  alco- 
hol, percolation  in  each  case  being  carried  on  until  the  liquid  passed 
tasteless.  The  alcohol  was  evaporated,  and  the  residues  were  treated 
with  water,  filtered  and  precipitated  by  a  solution  of  tannin.  These 
tannates  of  the  white,  grey,  and  black  roots,  which,  after  having  been 
dried,  weighed  respectively  "32,  '265,  and  "27  gram,  were  decomposed 
by  oxide  of  lead,  and  then  treated  with  alcohol,  in  order  to  separate 
colchicia.  The  three  alcoholic  solutions  were  carefully  evaporated 
to  dryness,  then  placed  over  sulphuric  acid  for  several  days,  and 
then  their  weight  taken  ;  the  product  from  the  grey  root  weighing 
•115  gram,  the  black  yielding  ^104  gram,  while  the  product  from 
the  white  root  was  unfortunately  lost. 

The  author  next  obtained  some  colchicum  root  from  Profes- 
sor Maisch,  which  was  not  less  than  ten  years  old,  it  having  been 
in  his  possession  at  least  nine  years.  It  had  quite  a  handsome 
appearance,  very  little  dark  root  being  present,  and  in  all  respects 
was  a  much  better  looking  article  than  that  previously  employed. 
Two  troy  ounces  of  this  root  were  treated  as  above  stated,  and  an 
acid  solution  obtained  measuring  100  c.c,  and  which,  when  treated 
with  ]\Iayer's  test,  in  a  similar  manner  as  before,  required  '0300  for 
the  precipitation  of  1  c.c. 

The  various  results  thus  obtained  are  more  concisely  presented  in 
the  followinof  table  : — 


White 
Root. 

Grey 
Boot. 

Black 
Root. 

Very  old 
Root. 

Mayer's  solution  required  to  precipitate 
1  c.c.  of  the  solution 

Percentage  of  alkaloid  in  air-dry  root  . 

Tauuate  precipitate  obtained  from  5 
troy  ounces  of  root 

Amount  of  crude  alkaloid  from  the 
tannates 

•403 
•205 

•320 

lost 

•414 
•210 

•265 

•115 

•492 
•219 

•270 

•104 

•0300 
•152 

230  TEAE-BOOK   OF   PHARMACY. 

From  this  table  it  will  be  seen  that  the  results  obtained  with  tannin 
and  Mayer's  solution  do  not  agree  as  to  the  amount  of  colchicine 
indicated.  This  may  be  due  to  the  slight  solubility  of  the  tannate 
in  water,  as  observed  by  liiibler  and  others,  and  to  the  yaiying 
amount  of  water  used  in  the  last  experiments.  But  the  results 
appear  to  indicate  that  it  matters  little  whether  the  root  has  a  white, 
grey,  or  black  colour ;  but  that  the  age  is  of  primary  importance, 
and  that  none  but  a  root  of  fresh  appearance  should  be  used  by  the 
pharmacist. 

ColcMcuni  Seed.  N.  Rosen wasser.  (From  an  inaugural  essay  : 
Amer.  Journ.  Pharm.,  1877,  435.)  The  author  prepared  the  active 
principle  of  the  seed,  and  found  it  to  have  a  neutral  reaction  to  test 
paper,  and  to  be  not  precipitated  from  aqueous  solutions  or  solutions 
acidulated  with  organic  acids,  by  potassio-mercuric  iodide,  sodium 
phospho-tungstate,  auric  chloride,  phosphomolybdic  acid,  and  solu- 
tion of  iodine,  all  of  which  reagents  afforded  precipitates  after  the 
solution  had  been  acidulated  with  a  mineral  or  oxalic  acid,  or  had 
been  boiled  for  a  few  minutes  with  acetic  acid.  [Ludwig  (1862) 
obtained  a  thick  precipitate  with  auric  chloride,  readily  soluble  in 
excess,  and  Eberbach  (1874)  found  the  aqueous  solution  of  his 
colchicia,  which  had  a  distinct  alkaline  reaction,  to  be  precipitated 
by  the  three  last  reagents  mentioned  above.]  The  author  argues 
from  this  that  .the  principle  is  naturally  neutral,  and  is  converted 
into  an  alkaloid  by  the  influences  mentioned.  The  neutral  sub- 
stance, colchicin,  was  with  some  difficulty  obtained  in  crystals  by 
the  slow  evaporation,  in  deep  vessels,  of  its  solutions  in  fusel  oil  and 
benzol,  and  found  to  be  insoluble  in  pure  ether,  carbon  bisulphide, 
and  petroleum  benzin. 

It  having  been  asserted  that  the  active  principle  resided  chiefly 
in  the  outer  integuments  of  the  seed,  and  that  for  this  reason  they 
could  be  almost  completely  exhausted  without  being  ground,  the 
author  experimented  with  5000  grains  of  unbroken  seeds,  macerated 
them  in  dilated  alcohol  in  a  warm  place  for  ten  days,  and  washed 
them  well  with  diluted  alcohol ;  the  tincture  and  washings  were 
used  for  preparing  colchicin  by  Carter's  process  (^Amer.  Journ. 
Fharm.,  1858,  p.  205),  of  which  five  grains  were  obtained.  The 
same  seeds  afterwards  crushed  to  an  uniform  powder,  yielded  eleven 
grains  of  colchicin.  5000  grains  of  seeds  of  the  same  lot  were 
ground,  and  yielded  sixteen  grains  ;  and  14,000  grains  of  the  same 
seeds,  rolled  and  crushed,  yielded  forty-five  grains  of  colchicin.  It 
follows,  therefore,  that  only  less  than  one-third  of  the  colchicin 
present  can  be  exhausted  from  the  unbroken  seeds.     In  preparing 


MATERIA    MEDICA.  231 

colchicin,  particularly  in  warm  weather,  it  is  found  unnecessary  to 
remove  the  fixed  oil  by  filtration  previous  to  precipitating  the  col- 
chicin  by  tannin ;  it  is  better  to  collect  the  precipitate,  dry  it  care- 
fully by  means  of  a  water  bath,  and  then  exhaust  the  oil  by  gasolin. 
For  the  decomposition  of  the  tannate,  aluminium  hydrate  seems  to 
possess  decided  advantages  over  ferric  or  plumbic  hydrate,  it  serv- 
ing at  the  same  time  as  a  decolorizing  agent. 

When  distilling  the  alcohol  for  the  tincture,  the  odour  of  the 
ground  seed  was  distinctly  recognised  in  the  distillate,  which  turned 
milky  upon  the  addition  of  water.  On  distilling  a  pound  of  the 
ground  seeds  with  water,  an  aromatic  distillate  was  obtained ;  but  a 
volatile  oil,  which  probably  exists  in  minute  quantity,  could  not  be 
separated.  The  distillate  was  tested  for  alkaloids  with  a  negative 
result. 

Fliickiger  and  Hanbury  give  G'G  per  cent,  as  the  amount  of  fixed 
oil  present  in  the  seeds ;  the  author  obtained  14  drams  (8-4  per 
cent.)  from  10,000  grains  of  the  seeds.  After  purifying  it  by  treat- 
ment with  benzin  and  animal  charcoal,  it  had  a  light  brown  colour 
and  a  bland  taste.     It  was  found  to  be  readily  sapouifiable. 

Pao  Pereira.  MM.  Rochefontaine  and  De  Freitas. 
(Pharm.  Journ.,  from  Compfes  Eendiis,  Ixxxv.,  412.)  The  pao-per-eira 
tree  is  a  native  of  Brazil,  and  its  bark  has  been  much  used  by  the 
physicians  of  that  country  since  Professor  Silva,  about  the  year  1830, 
made  known  its  febrifuge  and  antiperiodic  properties.  It  belongs 
to  the  Apocynacese,  and  has  been  variously  designated  as  Picramnia 
ciliata,  Vallesia  'punctata,  Talerncemontana  Icevis,  and  Geissospermum 
Vellosii.  Professor  Baillon  is,  however,  of  opinion,  after  a  recent 
examination  of  leaves  and  stems  received  from  Brazil,  that  it  should 
bear  the  name  of  Geissospermum  Iceve. 

The  bark  of  this  plant  contains  an  alkaloid  in  great  abundance ; 
this  was  first  extracted  in  1838  by  Santos,  and  called  by  him  "  perei- 
rine,"  but  the  authors  propose  to  change  this  name  to  "  geissosper- 
mine,"  after  the  generic  name  of  the  plant. 

The  dried  leaves  at  the  disposal  of  the  authors  had  an  extremely 
bitter  taste,  analogous  to  that  of  Quassia  amara,  which  became 
manifest  after  chewing  them  for  a  few  seconds.  This  state  being 
similar  to  that  of  the  stem  bark  suggested  the  presence  of  a  certain 
pi-oportion  of  alkaloid  in  the  leaves.  Some  leaves  were  therefore 
macerated  in  dilute  alcohol,  and  from  the  liquor  thus  obtained  an 
alkaloid  was  obtained,  as  was  a  similar  one  also  from  an  aqueous 
macei-ation  of  bruised  leaves.  It  seems  therefore  that  the  leaves 
contain  the  alkaloid,  though  in  less  quantity  than  the  bark,  and  this 


232  YEAR-BOOK    OF    PHARMACY. 

is  confirmed  by  the  physiological  action  of  the  aqueous  extract  of 
the  leaves  on  frogs. 

The  alkaloid  of  Geissospermnm,  as  employed  in  Brazil,  is  rot  a 
chemically  pure  product ;  it  occurs  under  the  form  of  a  brownish 
yellow  amorphous  powder,  the  bitterness  of  ■which  resembles  that 
of  the  leaves  and  the  bark.  Although  daily  employed  in  Brazil  for 
many  years  past,  the  physiological  action  of  neither  the  alkaloid  nor 
the  bark  appears  to  have  been  studied  experimently.  The  authors 
therefore  took  up  the  investigation,  using  geissosjiermine  dissolved 
in  -water  or  alcohol,  and  alcoholic  and  aqueous  extracts  of  the 
powdered  bark. 

The  experiments  showed  that  geissospcrmine  is  a  toxic  substance, 
exercising  no  local  irritant  action  when  administered  subcutaneously. 
Two  milligrams  introduced  under  the  skin  caused  the  death  of  a 
frog  ;  paralysis  was  produced  by  half  a  milligram.  A  full-grown 
guinea-pig  v?as  killed  by  one  centigram,  and  fourteen  centigrams 
completely  paralysed  a  small  dog.  The  symptoms  were  a  slacken- 
ing of  the  cardiac  beats,  and  of  the  respiratory  movements.  The 
voluntary  movements  were  first  paralysed,  the  reflex  movements 
gradually  ceasing  subsequently.  The  sensitive  nerves  appeared  to 
preserve  their  functions  as  long  as  the  motor  nerves.  The  muscular 
contractility  was  not  affected.  The  authors  therefore  consider 
geissospei'mine  to  be  a  poison  which  acts  by  destroying  the  physio- 
logical properties  of  the  central  nervous  grey  matter. 

Indian  Bmgs.  W.  Dymock.  (Pharm.  Journ.,  3rd  series,  vii., 
3,  109,  170,  190,  309,  350,  450,  491,  549,  729,  977.)  This  is  a  most 
important  contribution  to  pharmaceutical  literature,  embracing  as 
it  does  a  description  of  a  very  large  number  of  Indian  medicinal 
plants.  Owing  to  the  great  length  of  the  report,  which  is  not  yet 
concluded,  and  its  unsuitability  for  useful  abstraction,  we  must 
confine  ourselves  here  to  a  mere  reference  to  the  original. 


PHARMACY. 


PART   III. 
PHARMACY. 

Emulsions.  E.  Gregory.  (From  a  paper  read  before  the  Ameri- 
can Pharmaceutical  Association.)  The  following  are  the  results  of 
the  authoi''s  experiments  made  with  the  object  of  testing  the  merits 
of  the  various  processes  employed  in  making  emulsions : — 

1.  The  method  which  directs  that  equal  parts  of  mucilage  of  acacia 
and  oil  should  be  put  into  a  bottle  and  well  shaken  together,  the 
requisite  quantity  of  water  being  gradually  added.  If  the  mucilage 
be  fresh,  the  bottle  only  partially  full,  and  the  shaking  very  vigor- 
ous,  tolerable  results  can  be  obtained  "with  castor  oil,  moderate  re- 
sults with  balsam  copaiba,  and  -with  oil  of  turpentine  a  total  failure. 
But  in  all  eases  the  oil  globules  are  distinctly  visible  to  the  naked  eye. 

2.  Equal  parts  of  oil  and  mucilage  are  put  into  a  mortar  together, 
and  briskly  triturated.  This  gives  barely  tolerable  results  with  the 
balsams  and  thicker  oils ;  but  "with  oil  of  turpentine  it  is  a  total 
failure,  no  amount  of  labour  producing  the  slightest  effect. 

3.  Equal  parts  of  oil  and  mucilage,  the  oil  to  be  gradually  added,, 
triturating  briskly  after  each  addition  until  the  portion  added  is 
emulsified.  A  fair  result  can  be  obtained  by  this  process  if  the 
operator  have  plenty  of  patience  and  a  liberal  supply  of  muscle;  but 
the  product  is  too  dark  in  colour.  The  oil  globules  are  not  -visible 
to  the  naked  eye,  but  can  be  easily  seen  with  a  magnifying  power  of 
three  diameters.  It  separates  into  two  layers  in  two  and  a  half  hours, 
the  lower  layer  being  dark  but  not  watery. 

4.  The  next  process  is  that  wherein  equal  parts  of  mucilage,  water, 
and  oil  are  put  into  a  suitable  vessel,  and  agitated  with  an  egg-beater 
until  emulsionized.  This  yields  a  tolei'able  result,  is  simple,  and 
requires  no  skill,  but  is  rather  laborious,  and  yields  a  product  very 
dark  in  colour.  The  oil  globules  are  not  visible  to  the  naked  eye, 
but  quite  distinctly  under  a  power  of  three  diameters.  It  separates 
into  two  layers  in  three  hours,  the  lower  layer  being  very  watery. 

5.  The  next  process  tried  was  that  of  Mr.  Charles  P.  Hartwig 
(published  in  the  Pharmacist,  October,  1875),  in  which  one  part  of 
mucilage  and  one  part  of  water  are  put  into  a  suitable  ve.s.se], 
thoroughly  mixed  by  being  drawn  up  into  and  ejected  from  a  small 


236  YEAR-BOOK    OF    PHARMACY. 

vaginal  syringe,  and  one  part  of  oil  having  been  added,  tlie  emulsion 
is  produced  by  the  use  of  the  syringe  alone  in  the  same  way.  This 
process  yields  excellent  results,  but  the  emulsion  is  not  quite  as 
white  as  it  should  be ;  the  process  is  rather  tedious,  and  the  after- 
cleaning  very  troublesome.  It  is  the  best  of  the  processes  in  which 
oflBcinal  mucilage  is  employed.  The  oil  globules  are  invisible  to  the 
naked  eye,  but  are  distinctly  seen  with  a  power  of  three  diameters. 
It  separates  into  two  layers  in  twenty  hours,  the  lower  layer  being 
milky  in  appearance. 

G.  A  process  published  in  the  Journal  of  Pharmaaj,  in  February, 
1872,  by  ^Ir.  J.  Winchell  Forbes,  and  apparently  designed  more 
especially  for  oil  of  turpentine,  in  which  he  directs  that  one  part  of 
oil  shall  be  put  into  a  bottle  and  shaken,  then  one-eighth  part  of 
pulverized  acacia,  and  after  thorough  agitation,  half  a  part  of  water 
added,  the  whole  to  be  then  vigorously  shaken  until  emulsified. 
The  resulting  emulsion  is  deficient  in  whiteness.  The  oil  globules 
are  distinctly  visible,  as  a  multitude  of  gem-like  points,  under  a  mag- 
nifying power  of  three  diameters,  and  are  also  visible  to  the  naked 
eye  if  a  drop  be  placed  on  a  piece  of  glass  and  held  up  between  the  eye 
and  the  Hglit.  It  separates  into  two  distinct  layers  in  fifteen  minutes, 
the  lower  layer  being  quite  watery,  but  it  easily  reunites  on  shaking. 

7.  If,  however,  in  the  preceding  process,  three-eighths  of  a  part 
of  pulverized  acacia  be  used  instead  of  one-eighth,  a  very  good  re- 
sult is  obtained,  the  product  being  much  whiter,  the  oil  globules 
about  half  the  size,  and  quite  invisible  to  the  naked  eye.  It  now 
takes  twelve  hours  to  separate  into  two  layei'S,  the  lower  layer,  how- 
ever, being  still  watery. 

8.  The  next  process  for  consideration  is  described  on  page  343 
of  "  Mohr  and  Redwood's  Pharmacy,"  English  edition  of  1849,  in 
which  one  part  of  pulverized  acacia  and  one  and  a  half  part  of  water 
are  put  into  a  mortar,  and  after  thorough  trituration  three  parts  of 
oil  are  added  gradually,  each  separate  portion  being  emulsified  before 
another  is  added.  The  results  are  admirable,  the  product  being 
white  as  milk.  The  oil  globules  are  not  visible  to  the  naked  eye, 
but  slightly  so  under  a  power  of  three  diameters,  and  it  does  not 
separate  into  two  layers  under  twenty-four  hours,  the  lower  layer 
having  the  appearance  of  milk. 

9.  The  last  process  referred  to  is  recommended  by  Mr.  Hans 
M.  Wilder,  in  the  Druggists'  Ciradar  for  December,  1874.  One 
pai"t  of  pulverized  acacia  and  two  parts  of  oil  are  put  into  a 
mortar  and  rubbed  together;  one  and  a  half  part  of  water  is 
then  added  at  once,  and  with  a  few  revolutions  of  the  pestle  the 


PHARMACY.  237 

■whole  is  emulsified.  It  appears  to  yield  tlie  very  best  results.  The 
emulsion  is  beautifully  white,  scarcely  to  be  distinguished  from 
milk,  and  the  necessary  manipulations  are  very  speedy  and  simple. 
The  oil  globules  are  totally  invisible  to  the  naked  eye,  and  not  very 
perceptible  with  a  power  of  three  diameters.  It  separates  into  two 
layers  in  twenty-four  hours,  the  lower  layer  being  quite  like  milk, 
whilst  the  upper  would  pass  for  cream ;  and  at  the  time  of  writing 
this,  four  days  after  making,  retains  the  same  appearance,  and  is  by 
far  the  best  out  of  six  samples  that  are  standing  undisturbed  before 
the  author. 

In  summing  up  his  results,  the  author  states  that  the  use  of  muci- 
lage should  be  abandoned  in  favour  of  powdered  gum.  He  thinks 
that  three  drams  of  acacia  in  fine  powder  are  necessary  to  emul- 
sify one  ounce  of  any  of  the  volatile  oils,  and  that  a  little  less  (about 
two  drams)  will  answer  for  the  fixed  oils  and  balsams.  And  that 
to  this  quantity  of  gum  four  drams  and  a  half  of  water  must  be 
added  (no  more  and  no  less),  and  that  either  the  water  or  the  oil 
may  be  added  first  to  the  gum,  but  it  is  quickest  to  add  the  oil  first, 
and  well  triturate  before  adding  the  water.  Less  gum  can  be  made 
to  yield  a  good  result  by  a  careful  operator;  but  as  a  general  practi- 
cal working  rule,  it  may  be  said  that  three  drams  are  necessary 
for  one  ounce  of  oil. 

Officinal  Tinctures.  B.  F.  Mclntyre.  (A  contribution  to  the 
literature  of  the  proposed  International  Pharmacopoeia.  From  a 
paper  read  before  the  Alumni  Association  of  the  College  of  Phar- 
macy, N^ew  York.)  Percolation,  in  the  writer's  opinion,  is  an  unex- 
ceptionable process,  if  conducted  with  care  and  skill.  The  British 
Pharmacopoeia  directs  maceration  of  the  drug  with  only  a  portion 
of  the  menstruum,  the  residue  to  be  freed  from  tincture  and  extrac- 
tion by  percolation  with  fresh  spirit  until  a  prescribed  measure  is 
obtained. 

The  German  process,  which  like  that  of  the  French  Codex,  con- 
sists in  the  maceration  of  the  drug  with  the  full  quantity  of  men- 
struum, would  be  more  in  harmony  with  other  authorities  if  a  definite 
measure  or  weight  of  tincture  could  be  got  from  the  specified  parts 
of  the  drug ;  the  diiference  now  is  considerable  where  force  from 
handscrew  or  hydraulic  press  is  applied  to  the  expression  of  marc  or 
residue.  This,  however,  is  only  an  economic  point  for  consideration. 
The  loss  may  be  seen  in  the  annexed  table,  by  comparing  the  actual 
weight  of  tincture  obtained  from  the  drug  after  maceration  with  the 
theoretical  quantity,  or  the  proportional  medicinal  strength  of  the 
finished  tincture  given  in  the  next  column. 


238 


YEAPw-BOOK    OF    PHARMACY. 


In  the  experiments  tabulated  below,  the  manipulations  directed 
by,  and  characteristic  of,  the  several  pharmacopoeias  were  followed, 
though  the  menstrua  for  the  exhaustion  of  the  drug  were  disregarded, 
except  when  they  were  of  the  same  spirit  strength  as  that  designated 
in  the  U.  S.  P.  This  was  necessary  in  order  to  sustain  the  object  of 
this  paper,  the  finding  of  the  exact  parts  by  weight  of  tincture ;  the 
determinations  being  based  on  repeated  experiments  and  calculations 
made  from  weighings  of  hundreds  of  gallons  of  officinal  tinctures. 

As  the  German  Pharmacopoeia  specifies  that  tincture  of  belladonna 
and  digitalis  be  prepared  from  the  fresh  herb,  calculation  was  made 
for  loss  in  the  drying  of  the  hei"b,  and  the  powdered  drug  was  used 
instead. 


Parts  by  Weight  of  Tincture  containing  the  Soluble  Portion  of 

One  Part 

BY  Weight  of  Drug. 

Tincture. 

U.  S.  P. 

B.  P. 

German  Pharm. 

Prencli 
Codex. 

Aconite  Eoot     .... 

213 

6-71 

11 
9-30 

t 
10 

5-00* 

Belladonua 

7-20 

19-18 

7-62 

— 

5-00 

Cannabis  ludica     .     .     . 

17-80 

15-54 

20-00 

20 

— 

Calisaya  Bark  .... 

4-67 

4-74 

4-12 

5 

5-00 

Cautharides       .... 

28-25 

76-26 

9-36 

10 

10-00* 

Colchicum  Seed    .     .     . 

7-09 

7-33 

9-08 

10 

10-00* 

Foxglove 

7-30 

7-73 

5-95 

— 

5-00 

Ginger      .     .     .     ."  .     . 

3-16 

6-24 

4-88 

5 

5-00 

Henbane  

7-29 

7-64 

— 

— 

5-00 

Lobelia 

712 

7-61 

8-85 

10 

5-00 

Nux  Vomica 

3-15 

8-41 

8-97 

10 

5-00* 

Veratrum  Viride    .     .     . 

1-59 

3-63 

Ext.  of 
Opium. 

Opium 

11-52 

12-88 

9-30 

10 

12-00* 

Stramonium  Seed  .     .     . 

7-21 

7-65 

9-28 

10 

— 

Valerian 

7-13 

7-68 

4-79 

5 

5-00 
Ext.  of 

Opium  Camphorated. 

Opium. 

Opium,  Powdered      .     . 

234-24 

207-50 

198-00 

200 

215-00 

Benzoic  Acid     .... 

234-24 

207'50 

49-50 

50 

215-00 

Gum  Camphor  .... 

315-36 

276-66 

99-00 

100 

323-00 

Oil  of  Anise 

257-86 

138-33 

99-00 

100 

215-00 

Honey 

14-66 

— 

— 

— 

— 

Cinchona  Compound. 

Cinchona  Bed   .... 

8-68 

9-35 

11-62 

— 

— 

Orange  Peel       .... 

11-50 

18-74 

34-87 

— 

— 

Serpentaria 

46-00 

37-56 

— 

— 

Saffron 

— 

154-69 

— 

— 

Cochineal 



309-38 

— 

— 

— 

Gentian 



34-87 

— 

— 

Cassia 

— 

— 

69-74 

— 

— 

Aloes. 

Aloes  Soct 

30-82 

38-16 

5-90 

— 

— 

Liquorice  Extract.     .     . 

10-27 

12-58 

— 

— 

PHARMACY. 


239 


Tincture. 


Benzoin  Compound. 

Benzoin 

Soct.  Aloes      .... 

Storax   

Balsam  Tolu  .... 

Cardamom  Compound. 

Cardamom      .... 

CaraTvay 

Ciuuamon 

Cochineal  

Honey 

Eaisins 

Aloes  and  Mijrrh. 

Aloes      

Myrrh 

Catechu. 

Catechu 

Cinnamon       .... 

Gentian  Compound. 

Gentian 

Orange  Peel    .... 
Cardamom      .... 
Rhubarb. 

Ehubarb 

Cardamom 

Coriander 

Saffron 

Rhubarb  and  Senna. 

Ehubarb 

Senna    

Coriander 

Fennel 

Liquorice 

Eaisins 


u.  s.  p. 

B.  P. 

10-12 

9-80 

60-76 

53-60 

14-23 

13  09 

30-38 

39-67 

48-70 

78-40 

145-83 

78-40 

58-33 

39-20 

291-66 

142-43 

18-22 

1 

— 

9-76 

9-26 



9-26 

— 

9-64 

14-47 

— 

14-36 

13-06 

28-72 

26-15 

57-44 

78-49 

9-69 

9-71 

58-17 

77-98    1 

— 

77-98 

— 

77-98 

1 

43-75 

175-00 

— 

350-00 

— 

350-00 

— 

700-00 

— 

21-87 

— 

Tincture. 


Iodine  Compound. 

Iodine 

Iodide  of  Potassium  . 

Assafoetida  .... 

Arnica 

Benzoin 

Bloodroot  .... 
Black  Hellebore  .  . 
Capsicum     .... 

Conium 

Castor 

Cardamom  .... 
Cinnamon    .... 

Columbo 

Cubeb      

Guaiac 

Guaiac  Ammoniated. 

Galls 

Hop 

Jlron       

Iodine 

Jalap 

Kino 

Lupulin 

Myrrh 

Opium  Deodorized  . 
Opium  Acetated   .     . 

Quassia 

Orange  Peel     .     . 

Ehatany 

Serpentaria      .     .     . 

Squill 

Tolu 

Valerian  .... 
Valerian  Ammoniated 


U.  S.  P. 


28  07 
14-07 

6-35 

4-86 
4-81 
7-12 
7-29 

28-00 
6-97 

12-76 
7-06 
8-96 
7  13 
7-19 
4-41 
4-86 
7-44 
5-69 


13-53 
4-75 
9-49 
6-43 
8-38 

12-50 
9-27 

13-97 
7-30 
4-86 
7-16 
7-46 
9-69 
7-13 
6-60 


I  One  fluid  dram  of  tincture  of  iron,  U.  S.  P.,  contains  3-53  grains  of  oxide  of 
iron.  One  fluid  di-am  of  the  same  tincture,  B.P.,  contains  3*90  grains  of  ferric- 
oxide. 

[\  Parts  by  weight  of  tinctm-e  actually  obtained  from  one  part  by  weight  of 
the  drug. 

+  Parts  by  weight  containing  the  active  principles  of  one  part  by  weight  of 
the  drug. 

*  Tinctures  directed  to  be  made  by  maceration. 


A  New  Application  of  Dialysis.  R.  Rot  her.  {Pharmacist, 
January,  1877.)  In  the  article  on  "  The  Inverse  Synthesis  of  the 
f=o-called  Tasteless  Iron  Componnds  "  {American  Journal  ofFliarmacy, 
April,  1876),  the  author  pointed  out  the  important  fact,  that  in 
particular  cases  of  colloidal  compounds  the  endosmotic  current  is 


240 


YEAR-BOOK   OF    PHARMACY. 


the  most  prominent  feature  of  the  movement.  On  such  occasions 
the  inward  course  of  the  outer  liquid  appears  to  be  the  only  force 
of  the  phenomenon,  since  exosmosis  prevails  so  feebly  that  practically 
its  effect  is  reduced  to  zero.  The  rapidity  of  the  endosmotic  current 
gives  promise  that  a  new  development  of  this  interesting  and  re- 
markable process  will  lead  to  great  advantages  in  numerous  and 
important  pharmacal  operations.  This  peculiarity  presents  a  new 
means  of  concentrating  solutions  where  the  absence  of  heat  is  not 
only  desirable,  but  often  imperative.  In  its  practical  bearing  this 
method  of  transcendental  filtration  presents  a  wide  range  of  applica- 
tion, which  must  be  classified,  however,  as  entirely  distinct  from  the 
present  sense,  and  the  theoretical  action  in  which  the  process  is 
usually  considered.  The  residue,  technically  called  the  diffusate,  is, 
according  to  the  original  idea  of  this  process,  a  solution  of  the 
diffused  substance.  The  residue  of  the  new  modification  differs 
from  the  diffusate  proper  in  the  particular  that  it  practically  contains 
nothing  originally  introduced  into  the  dialyser,  but  that  it  simply 
represents  that  portion  of  the  original  outer  liquid  which  refused 
to  pass  inwards  through  the  membrane.  Therefore,  according  to 
the  new  construction,  the  process  resembles  filtration  more  closely 
than  its  primitive  process  from  which  it  is  derived.  In  some 
instances  it  is  even  more  rapid  than  ordinary  filtration.  Absorption 
in  this  operation  corresponds  with  volatilization  in  the  usual  method 
of  concentration  by  means  of  heat.  As  the  action  of  heat  produces 
undesirable  and  often  destructive  changes  in  many  substances, 
even  at  the  lowest  possible  degree,  the  process  of  dialytic  filtration 
must  naturally  commend  itself  on  all  such  occasions,  where  its  ap- 
plication is  available.  If  the  point  of  a  parchment  dialysing  cone 
containing  a  concentrated  solution  of  strongly  colloidal  substance 
be  immersed  in  a  dilute  solution  of  a  ci'ystalloitl,  the  superabundant 
water  of  the  latter  is  more  or  less  rapidly  absorbed  into  the  dialyser, 
leaving,  after  due  action,  the  solution  of  the  crystalloid  in  its  utmost 
concentration.  It  is  possible  that  this  process  may  become  useful 
in  the  industrial  production  of  alkaloids,  where  in  the  usual  method 
laro-e  volumes  of  water  must  be  expelled  by  means  of  heat,  the  action 
of  which,  in  many  cases,  greatly  reduces  the  yield  by  the  generation 
of  inert  modifications  or  worthless  disruption  products.  This  pro- 
cess, with  its  accompanying  apparatus,  is  more  congenial  to  the 
surroundings  of  modern  pharmacal  laboratories  in  which  the  routine 
is  less  interspersed  with  the  manipulation  of  distrustful  retorts, 
precarious  capsules,  and  fuming  crucibles  of  the  empiric  era.  It 
would  be  hardly  proper  to  designate  this  process  dialysis,  since  that 


PHARMACY,  241 

term  specifically  denotes  an  operation  not  exactly  similar.  Absorp- 
tion also  does  not  strictly  convey  the  true  meaning  of  its  action ; 
however,  in  case  the  new  process  should  prove  itself  of  such  general 
value  as  the  first  indications  seem  to  promise,  a  more  appropriate 
term  will  readily  be  found. 

The  Preparation  of  Pyroxylin  for  Photographic  and  Pharma- 
ceutical Purposes.  W.  Godeffroy.  (Zeltschrift  des  oesterr.  Apoth. 
Ver.,  1877,  209.)  Most  of  the  published  formula?  for  the  pro- 
duction of  pyroxylin  yield  a  preparation  which  does  not  form  a 
perfectly  clear  solution  with  ether,  or  a  mixture  of  ether  and 
alcohol.  From  the  author's  experience  it  appears  to  be  advan- 
tageous to  employ  the  acid  mixture  at  a  slightly  elevated  tempera- 
ture. He  uses  potassium  nitrate  and  sulphuric  acid  in  the  pro- 
portion of  350  grams  of  the  former  and  700  grams  of  the  latter  to 
35  grams  of  cotton.  A  porcelain  mortar  is  gently  warmed  on  a 
sand  bath,  and  the  powdered  saltpetre  triturated  in  it  until  it  is 
perfectly  dry ;  the  sulphuric  acid  is  then  added,  and  intimately 
mixed  with  the  saltpetre,  and  the  cotton  immersed  without  remov- 
ing the  mortar  from  the  bath.  The  cotton  is  first  freed  from  fatty 
matter  by  heating  it  in  a  solution  of  sodium  carbonate,  then  boiling 
it  with  water  to  which  a  minute  quantity  of  caustic  potash  has  been 
added,  9,nd  finally  washing  it  with  pure  water  until  the  alkali  is 
completely  removed.  Thus  purified,  and  again  dried,  it  is  intro- 
duced into  the  acid  mixture,  well  kneaded  with  it  by  means  of  a 
pestle,  and  left  immersed  for  seven  minutes.  After  this  time  it  is 
quickly  transferred  to  a  large  vessel  containing  hot  water,  then 
washed  under  a  stream  of  cold  water  until  the  acid  reaction  has 
entirely  ceased,  and  finally  with  distilled  water.  After  removing 
the  water  by  strong  pressure,  the  pyroxylin  is  ready  for  use,  and 
may  be  at  once  dissolved  without  further  drying. 

Mustard  as  a  Deodorizer.  F.  Schneider.  (Pharm.  Zeltung,  1877, 
119.)  The  author  calls  attention  to  the  value  of  black  mustard  as 
a  deodorizing  agent.  The  odours  of  cod-liver  oil,  musk,  valerian- 
ates, and  many  other  drugs,  can  be  rapidly  removed  by  it  from 
the  hands,  utensils,  scales,  etc.  The  farina  is  mixed  with  a  little 
water  before  it  is  applied. 

The  Dispensing  of  Copaiba  Resin.  A.  Balkwell.  (Pharm.  Journ., 
3rd  series,  vii.,  481.)  The  following  form  of  exhibiting  copaiba  resin 
has  been  found  to  give  satisfaction  both  to  prescriber  and  patient. 
It  is  easily  prepared,  and  the  mixture  in  appearance,  permanence,  and 
therapeutic  action  is  said  to  be  preferable  to  that  of  any  form  the 
writer  has  met  with  : — 


242 


TEAR-BOOK    OP    PHARMACY. 


9.    Eesinfe  Copaibre  . 

5133 

01.  Amygdal.  Dulc. 

5iv. 

Mucil.  Acaciaj 

3is3 

Liq.  Potassre 

3SS. 

01.  Cinnamomi     . 

gutta;  vi 

Aqnam          .... 

.     ad  5vi 

i.  sixth  part  three  times  a  day. 

Dissolve  the  resin  in  the  almond  oil  with  gentle  lieat,  then  add 
the  liq.  potassa),  and  form  an  emulsion. 

An  Improved  Method  of  Making  Mistura  Guaiaci,  and  Similar 
Mistura.  T.  Greenish.  (P//a/-»2.. /o?tr?i.,  3rd  series,  vii.,  309.)  The 
excipients  suggested  by  the  author  are  sugar  of  milk  and  alcohol, 
and  answer  well  with  resin  of  copaiba,  guaiacum,  and  other  resins. 
For  mistura  guaiaci,  he  recommends  to  rub  the  resin  with  surjar  of 
milk,  then  to  add  alcohol  and  to  produce  a  homogeneous  mixture  by 
trituration  ;  to  this  is  to  be  added  powdered  gum  arabic,  the  tritu- 
ration to  be  continued,  and  the'  water  gradually  added.  The  formula 
for  mistura  guaiaci  would  then  stand  thus : — 


R     Guaiacum  Resin  in  powder 
Sugar  of  Milk 
Gum  Acacia  in  powder  . 
Rectified  Spirit 
Cinnamon  Water    . 


\  ounce. 

^  ounce. 

^  ounce. 
5  fluid  drams. 
.  to  one  pint. 


The  following  formula  affords   an  example  of  a  good  emulsion 
of  copaiba  resin  : — 


9>     ResiniB  Copaibse 
Sacch.  Lactis 
Spirit.  Vini  Rect 
Pulv.  Acaciae 
Aquae  ad 


5"J- 

Jvj.     Misce. 


Pepsin  and  its  Preparation.  Dr.  0.  Liebreich.  (Neiu Bemedies, 
from  the  Practitioner,  March,  1877.)  In  a  valuable  paper  on  "The 
Use  of  Pepsin  in  Medicine,"  the  author  refers  to  the  attempts  that 
have  been  made  to  employ  the  peptones  as  therapeutic  digestive 
agents,  and  their  failure  owing  to  the  rapidity  with  which  they  under- 
go decomposition.  He  expresses  his  belief  that  the  field  of  usefulness 
of  pepsin  in  practical  therapeutics  is  very  great,  and  that  it  may  be 
still  further  extended  with  very  great  advantage.  But  the  success 
of  this  remedy  has  been  greatly  hindered,  and  the  result  of  clinical 
and  of  scientific  experiment  as  to  the  results  which  may  be  obtained 
have  been  much  confused  by  the  number  of  comparatively  worthless 
preparations  which  have  been  employed,  and  by  the  instability  and 


PHARMACY.  243 

nncertainty  of  some  of  those  preparations  wbich  in  their  most 
active  states  have  from  time  to  time  yielded  excellent  results,  and 
have  thus  attained  a  good  reputation.  The  uncertainty  of  a  potent 
remedy  is  almost  as  injurious  and  even  more  misleading  than  the 
inertness  of  a  popular  remedy,  and  the  treatment  of  disorders  of 
digestion  by  pepsin  has  suffered  greatly  from  both  these  drawbacks 
and  from  both  these  sources  of  fallacy. 

Following  the  description  of  a  number  of  conditions  in  which  the 
employment  of  pepsin  as  a  remedy  is  calculated  to  be  of  benefit  to 
the  patient,  the  author  remarks  that  there  are  certain  counter  indi- 
cations of  the  use  of  pepsin,  to  which  it  may  be  well  to  refer.  Among 
them  are  carcinoma  and  ulceration  of  the  stomach.  When  there  is 
an  ulcer  of  the  stomach  it  is  an  object  of  treatment  to  afford  a  smooth 
covering  to  the  ulcer  by  bismuth,  or  by  the  administration  of  nitrate 
of  silver ;  to  administer  pepsin  is  to  incur  the  risk  of  hastening  the 
process  of  thinning,  which  there  is  already  too  much  reason  to  fear 
from  the  action  of  the  normal  pepsin  of  the  stomach. 

To  fulfil  the  therapeutical  indication  of  pepsin  it  is,  however, 
necessary  to  have  a  pure  and.  reliable  sample.  There  are  various 
methods  of  obtaining  the  article.  Thus,  there  is  the  method  of 
Brlicke,  by  treating  the  gastric  juice  (obtained  by  well-known 
methods),  with  a  solution  of  cholesteriue  in  ether;  the  cholesterine, 
being  precipitated,  enters  into  naechanical  combinations  with  the 
pepsin,  and  pure  pepsin  is  obtained  by  removing  the  cholesterine  by 
the  further  addition  of  ethei'. 

This  form  of  dry  pepsin  is  absolutely  pure,  and  from  it  may  be 
learned  the  qualities  and  powers  of  pepsin.  But  the  method  is  too 
costly  for  general  use,  and  its  advantages  are  mainly  for  scientific 
purposes.  There  are  various  dry  preparations  of  pepsin  in  powder 
and  cake,  which  are  well  known,  and  much  used  in  medicine.  Bat 
these  preparations  are  very  far  from  stable  or  reliable,  and  however 
active  some  of  them  may  be  when  perfectly  fre.sh,  they  do  not  re- 
main active,  and  a  large  part  of  the  pepsin  powders  pre,scribed  are 
absolutely  inert.  Pepsin,  although  an  albuminoid,  differs,  among 
other  things,  from  ordinary  albumen  in  being  soluble  in  diluted 
alcohol.  Advantage  has  been  taken  of  this  to  prepare  pepsin  wines, 
but  the  alcohol  does  not  prevent  the  ferment  from  undergoing 
change,  and  if  a  "  pepsin  wine  "  be  examined  after  some  time,  it  will 
be  found  not  to  contain  a  trace  of  pepsin,  and  to  be  absolutely  de- 
void of  digestive  power.  The  author  found,  many  years  ago,  that 
to  preserve  the  ferment  of  pepsin  there  is  only  one  reliable  agent, 
that  is  glycerin,  the  powerful  preserver  of  vaccine-matter  and  other 


244  YEAR-BOOK    OF    PHAKMACY. 

animal  ferments.  His  first  researches  on  this  subject,  made  many 
years  ago,  have  been  amply  confirmed  by  a  great  number  of  obser- 
vations, and  for  all  scientific  experiments  on  digestion  he  has  now  for 
many  years  employed  only  these  solutions.  He  strongly  recommends 
practitioners,  for  all  therapeutical  purposes,  to  employ  such  a  solu- 
tion. In  this  way  they  will  avoid  the  fallacies  and  disappointment 
due  to  the  employment  of  deceptive  and  unequal  preparations,  and 
they  will  the  more  readily  define  the  true  limits  of  pepsin  as  a 
therapeutic  agent,  and  its  place  in  the  armoury  of  medicine.  It  is 
not  to  be  reckoned  among  the  most  powerful  and  heroic  remedies, 
but  it  is  one  which  is  of  very  agreeable  and  efficacious  action  ;  which 
very  frequently  gives  exceedingly  good  results  in  large  classes  of 
ordinary  and  troublesome  complaints,  and  which  may  be  employed 
with  confidence  and  advantage  when  its  powers  are  stable  and  re- 
liable. 

The  Constituents  of  S3rrup  of  Phosphate  of  Iron.  E.  B.  Shuttle- 
worth.  (^Canadian  Pliarm.  Journ.,  August,  1876.)  During  the 
past  few  years  there  have  appeared  in  the  pharmaceutical  journals 
numerous  papers  and  notes  on  phosphate  of  iron  and  the  syrups 
containing  it.  The  author  in  the  present  essay  reviews  this  litera- 
ture, with  the  object  of  representing  in  as  concise  a  form  as  possible 
the  main  points  of  the  subject,  omitting  all  unessential  details. 

Phosphoric  Acid. — Of  this  substance  there  are  several  varieties. 
The  trihasic  acid,  having  the  composition  Hg  P  0^,  combining  weight 
98,  is  that  used  in  medicines.  In  order  to  distinguish  this  form 
from  the  others  add  a  little  tincture  or  solution  of  perchloride  of 
iron;  if  the  mixture  remains  clear  the  tri basic  acid  is  present,  other- 
wise a  whitish  precipitate  is  produced.  The  official  form  of  this  acid 
is  the  Acid.  Phosphoric.  Dilutiim,  but,  in  order  to  avoid  disappoint- 
ment it  is  always  well  to  submit  this  preparation  to  the  above  test. 
If  a  precipitate  is  produced,  boil  down  the  acid  to  the  consistence  of 
syrup,  allow  it  to  cool,  and  add  water  up  to  the  ordinary  bulk.  ]  f 
the  official  acid  is  not  at  hand  the  glacial  acid  may  be  substituted, 
being  previously  treated  with  nitric  acid  after  the  manner  of  the 
United  States  Pharmacopoeia.  This  will  not  always  furnish  the 
tribasic  acid,  and  simple  solution  and  evaporation  of  the  glacial  acid, 
without  the  addition  of  nitric  acid,  often  gives  as  good  results. 
Neither  method  can  be  relied  upon  with  all  samples  of  acid.  The 
prepai-ation  of  phosphoric  acid  from  phosphorus  should  never  be  at- 
tempted by  the  pharmacist.  The  process  requires  much  care  and 
experience,  is  not  economical,  except  with  large  quantities,  is  at- 
tended with  the  evolution  of  poisonous  and  disagreeable  gases,  and 


PHARMACY.  245 

like   all    operations     with    phospliorus,    is    always    more    or    less 
dangerous. 

For  preparing  syrups,  and  indeed  for  most  purposes,  an  acid 
stronger  than  that  official  (10  per  cent,  anhydrous  acid)  might  be 
advantageously  employed.  The  so-called  sijrvipy  acid,  which  can  be 
obtained  from  some  manufacturers,  and  which  is  about  five  times 
stronger  than  the  other  (49  per  cent,  anhydrous  acid,  and  of  sp.  gr. 
1"5)  will  be  found  very  useful. 

Phosphate  of  Iron. — Five  methods  have  been  recommended  for 
preparing  this  substance  : — (1)  By  mixing  together  solutions  of 
sulphate  of  iron  and  phosphate  of  soda ;  (2)  by  using  these  salts 
with  the  addition  of  acetate  of  soda ;  (3)  by  substituting  carbonate 
or  bicarbonate  of  soda  for  the  acetate  ;  (4)  by  employing  an  excess 
of  phosphate  of  soda  ;  (5)  by  forming  the  phosphate  by  direct  com- 
bination of  phosphoric  acid  and  metallic  iron.  By  the  first  method, 
which  is  that  of  the  United  States  Pharmacopoeia  and  Parrish's 
"  Pharmacy,"  about  30  per  cent,  of  the  phosphate  of  iron  escapes 
precipitation,  as  the  free  sulphui-ic  acid,  liberated  in  the  reaction, 
dissolves  or  holds  this  amount.  The  framers  of  the  British  Pharma- 
copoeia sought  to  escape  this  loss  by  employing  acetate  of  soda  for 
neutralizing  the  free  sulphuric  acid,  as  in  the  second  method.  This 
addition  has  been  shown  to  be  an  improvement,  but  is  still  in  great 
part  inefFectual,  as  from  22  to  28  per  cent,  of  the  phosphate  is  lost. 
In  the  third  method,  that  of  Mr.  Schweitzer,  in  which  carbonate  or 
bicarbonate  of  soda  is  employed,  the  loss  is  reduced  to  less  than  one 
per  cent.  The  fourth  method,  that  of  Mr.  Rees  Price,  is  said  to 
yield  results  equally  satisfactory,  but  nearly  three  times  the  usual 
quantity  of  phosphate  of  soda  is  required.  On  the  score  of  economy 
this  is  quite  a  consideration.  The  fifth  method,  that  of  direct  com- 
bination, answers  well  w^here  time  is  not  an  object.  If  acid  of 
sp.  gr.  I'D  be  used,  it  should  be  diluted  with  an  equal  weight  of 
water,  and  the  iron  should  be  in  the  form  of  filings,  preferably  of 
Swedish,  or  wrought  metal.  In  order  to  produce  a  preparation 
similar  to  the  Syr.  Ferri  Phosjjhatl.^;,  B.  P.,  and  containing  one  grain 
of  phosphate  in  each  fluid  dram,  the  following  formula  may  be 
employed : — 

Iron 38  grains. 

Phosphoric  Acid,  sp.  gr.  1-5    .         .        6  fluid  di-ams. 
"Water      ......        6     ,,  ,, 

Syrup      .         .         .         .         .         .    8J  fluid  ounces. 

Mix,  in  a  flask,  the  phosphoric  acid  and  water;  add  the  iron,  and 


246  YEAR-BOOK    OF    PHARMACY. 

plug  the  mouth  of  the  flask  with  cotton :  when  the  iron  is  clissolved, 
filter  the  solution  and  add  it  to  the  syrup. 

The  blue  phosphate  of  iron  is  not  a  substance  of  very  definite 
composition,  and  it  is  questionable  whether  the  above  methods 
furnish  compounds  cWhich  are  identical.  Even  when  the  same  in- 
gredients are  used  in  proportions  exactly  alike,  the  products  may 
differ  if  the  details  of  manipulation  be  changed.  In  all  cases  the 
intention  is  to  produce  ferrous  phosphate,  but  this  is  never  alto- 
gether accomplished,  as  a  great  portiou  of  the  salt  passes  to  the 
ferric  condition ;  or,  as  may  be  better  understood,  passes  from  a 
proto  to  a  per  salt.  An  analysis  of  six  samples  of  commercial  phos- 
phate showed  a  range  of  from  20  to  46  per  cent,  of  ferrous  salt.  It 
appears  likely  that  the  last  method  noted  above  would  yield  a  pre- 
paration richer  in  ferrous  salt  than  any  of  the  othei"s,  but  it  is  said 
that  the  third  method  gives  a  salt  containing  61  per  cent.,  which  is 
more  than  5  per  cent,  better  than  the  B.  P.  standard. 

Taking  everything  into  account,  the  author  much  prefers  this 
process,  and  has  used  it  with  satisfaction  for  several  years.  The 
proportions  of  the  sulphate  of  iron  and  phosphate  of  soda  as  given 
in  the  B.  P.  may  be  retained  ;  but  instead  of  one  ounce  of  acetate  of 
soda,  about  half  that  quantity  of  bicarbonate  of  soda  must  be  used. 
A  better  form  is  that  of  Mr.  Howie  : — 

Sulphate  of  Iron 7^  pai'ts. 

Phosphate  of  Soda 6^      ,, 

Bicarbonate  of  Soda .        .        .        .        .     1^      ,, 

Dissolve  the  sulphate  in  ten  times  its  weight  of  water,  which  has 
been  previously  boiled,  in  order  to  expel  air ;  and  the  phosphate  of 
soda  in  a  like  quantity,  similarly  treated.  Let  the  solutions  cool  to 
between  100°  to  lo5°  Fahr.,  and  pour  the  phosphate  very  gradually 
into  the  iron,  with  constant  stirring.  Add  the  bicarbonate,  either 
in  powder  or  solution.  Let  the  precipitate  subside  ;  decant ;  wash 
well  with  previously  boiled  water ;  collect  on  a  filter  and  squeeze 
out  as  much  water  as  possible,  either  with  the  hand  or  an  ordinary 
press.  These  details  of  manipulation  must  be  rigidly  adhered  to — 
more  especially  those  relating  to  the  order  of  mixing  and  tempera- 
ture— or  uniform  results  cannot  be  obtained.  If,  in  the  above 
formula,  the  parts  be  held  to  indicate  drams,  it  may  be  read  as 
part  of  Parrish's  receipt  for  the  so-called  chemical  food,  published 
in  his  "  Practical  Pharmacy,"  p.  425,  and  the  iron  strength  of  the 
resulting  preparation  will  accord  with  the  compound  sold  as 
genuine. 


PHARMACY.  247 

Sugar. — Some  Englisli  writers  have  enlarged  considerably  on  the 
importance  of  obtaining  pure  cane  sugar.  It  is  said  that  beet  sugar 
is  very  abundant  in  the  English  and  French  markets,  and  is  largely 
substituted  for  that  of  the  cane.  The  selection  of  a  pure  article  is 
a  matter  of  prime  importance,  as  many  of  the  pliarmacist's  troubles 
relating  to  the  fermentation  and  precipitation  of  syrups  are  refer- 
able to  impurities  in  the  sugar. 

The  Administration  of  Eousso.  Dr.  Corre.  (Bull,  de  Therap., 
1876,  556.)  The  following  method  is  intended  to  bring  kousso 
into  such  a  pharmaceutical  shape,  that  while  its  properties  as  a 
toenicide  remain  unimpaired,  it  may  be  administered  without  repug- 
nance. 

Treat  25  grams  of  powdered  kousso  with  40  grams  of  hot  castor 
oil,  and  afterwards  with  50  grams  of  boiling  water,  by  displacement; 
express,  and  combine  the  two  percolates  into  an  emulsion  by  means 
of  yolk  of  e^g.,  and  add  40  drops  of  sulphuric  ether.  It  may  be 
sweetened  with  syrup  and  aromatised  to  taste.  This  is  taken  at 
one  dose  early  in  the  morning.  The  worm  is  expelled  during  the 
third  or  fourth  evacuation,  after  about  six  or  eight  hours. 

Aqua  Laurocerasi.  A.  Ripping.  (Archiv  der  Pharm.,  Dec, 
1876.)  The  great  difference  in  the  effects  of  different  samples  of 
the  commercial  water  led  the  author  to  suspect  that  much  of  it  was 
prepared  artificially ;  in  order  to  examine  the  subject  he  prepared 
some  himself.  From  his  own  experiments  he  had  previously  ascer- 
tained that  each  litre  of  the  natural  distilled  cherry-laurel  water 
contained  about  three  grams  of  essential  oil.  Having  prepared 
some  dilute  hydrocyanic  acid,  of  the  strength  required  by  the  Phar- 
macopoeia for  cherry-laurel  water  (1  in  1000),  he  added  to  each 
litre  three  grams  of  oil  of  bitter  almonds,  and  obtained  a  mixture 
which  appeared  to  be  identical  with  the  natural  water.  To  distin- 
guish between  the  two  waters,  the  process  of  Mohr  for  distinguishing 
between  natural  and  artificial  bitter-almond  water  may  be  employed  ; 
namely,  silver  nitrate,  which  produces  only  a  slight  opalescence  in 
the  natural  water,  as  the  hydrocyanic  acid  is  wholly  fixed  by  benz- 
aldehyde,  and  the  opalescence  is  cau.sed  by  ammonium  cyanide,  which 
is  formed  diu'ing  the  distillation  by  the  splitting  up  of  the  hydrocy- 
anic acid  into  ammonia  and  formic  acid.  The  presence  of  nitrobeuzol 
may  be  recognised,  according  to  Hager,  by  shaking  the  water  with 
chloroform,  evaporating  the  latter,  treating  the  residue  with  alcohol 
and  water,  and  then  adding  zinc,  hydrochloric  acid,  and  after  a 
while  a  small  piece  of  potassium  chlorate.  If  no  change  of  colour 
takes  place,  the  absence  of  nitrobeuzol  is  proved,  as  the  latter  would 


248 


TEAR-BOOK    OF    PHARMACY. 


be  converted  by  nascent  hydrogen  into  anilin,  Tvhicli  would  be 
changed  to  rosanilin  by  potassium  chlorate,  and  would  tinge  the 
alcohulic  liquid  rose  red. 

Benzoic  Acid  as  an  Antiseptic.  H.  Trimble.  (Abstract  from 
an  inaugural  essay  :  Anter.  Joiirn.  Phann.,  Aug.,  1876,  347.)  For 
tlie  purpose  of  investigating  this  property,  claimed  for  benzoic  acid, 
two  samples  were  employed :  one  obtained  by  sublimation,  accord- 
ing to  the  U.  S.  P.  process,  and  the  other  purchased  under  the 
name  of  "artificial"  benzoic  acid,  supposed  to  have  been  prepared 
from  hippuric  acid.  A  good  commercial  salicylic  acid  was  also  pro- 
cured, which,  with  the  above-mentioned  samples,  formed  the  basis 
of  the  following  experiments,  in  one  half  of  which  both  the  sublimed 
and  artificial  benzoic  acids  were  used,  and  found  to  be  identical  in 
antiseptic  power ;  the  remaining  experiments  were  therefore  made 
with  the  artificial  acid  only.  The  results  of  the  writer  are  condensed 
in  the  following  table  : — 


One  part  of 


Salicylic 
acid 

Benzoic 
acid 


200n  parts 
Infusion 
Buchu 

SpoUed  in  8 
days 

Remained 
unaltered 
after  60 
days 


4000  parts 
Infosion 
Buchu 


Spoiled  in  4 


Spoiled   in 
16  days 


8000  parts 
Infusion 
Buchu 


Spoiled  in  5 
days 


2000  parts   ;  2000  parts   I  1000  parts     4000  pails 
Infusion        Infusion   |  Solution  of    Solution  of 


Colombo 


Gentian, 
simpl 


Albumen    j  Albumen 
[1  in  16  water] 


SpoiledinO   Spoiled  in   Spoiled   in    Spoiled    in 
days  I    19  days      I   12  days  10  days 

Cloudy.but  Unaltered  Unaltered     Spoiled    in 

no  change     after  30  i    after  00      \    19  days 

of  colour   I    days  days 
in  16  days  i 


To  ascertain  the  power  of  salicylic  and  benzoic  acids  to  arrest 
decomposition,  they  were  each  added  in  proportion  of  one  part  to 
2000  of  separate  portions  of  cider  which  had  commenced  to  ferment. 
In  both  cases  the  fermentation,  after  twenty-four  hours,  had  entirely 
ceased,  and  both  were  perfectly  sweet  at  the  end  of  fifty  days,  with- 
out the  appearance  of  any  further  decomposition,  a  rather  curious 
precipitate  having  separated  at  the  bottom  of  each. 

It  must  be  remembered  that  the  infusions  in  the  above  experiments, 
■without  the  addition  of  an  antiseptic,  would  have  commenced  to 
decompose  in  about  twenty-four  hours,  and  the  solution  of  albumen 
in  about  forty-eight  hours.  In  all  cases  the  operations  were  con- 
ducted in  a  moderately  warm  place,  so  as  to  favour  a  change  as 
rapidly  as  possible. 

Having  carefully  compared  the  above  experiments  and  their 
results,  the  following  conclu.^ions  are  submitted : — 

1.  That  benzoic  acid,  sublimed  or  artificial,  possesses  valuable 
antiseptic  properties. 


PHARMACY.  »         249 

2.  It  has  the  power  to  arrest  decomposition. 

3.  Tannic  acid  (of  buchu  ?)  does  not  interfere  with  its  preserva- 
tive properties.  . 

4.  As  an  antiseptic,  it  is  superior,  in  many,  if  not  in  all  cases,  to 
salicylic  acid.  It  also  has  the  advantages  of  being  more  readily 
obtained  in  a  state  of  purity,  of  being  more  soluble,  and  having 
a  lower  commercial  value. 

Chrysophanic  Acid  Ointment.  B.  Squire.  {Pharm.  Journ.,  3rd 
series,  vii.,  489.)  The  author  has  employed  goa  powder  as  an  applica- 
tion in  various  cutaneous  affections,  and  has  come  to  the  conclusion 
that  chrysophanic  acid,  which  is  the  chief  ingredient,  is  also  the 
active  agent  of  this  drug.  The  favomdte  mode  of  applying  goa  in 
the  tropics  seems  to  be  to  wet  the  powder  with  water,  or  with  viuegar 
or  lemon  juice,  and  to  smear  the  thin  paste  thus  produced  on  the 
affected  skin.  But  this  paste  dries  ap  very  speedily  into  its  original 
condition  of  fine  dry  powder,  which  is  easily  rubbed  off  by  the 
slightest  touch.  According  to  the  author,  an  ointment  is  unques- 
tionably a  much  better  form  of  applying  the  remedy.  This  form, 
seems  occasionally  to  have  been  had  recourse  to  ;  but  wetting  the 
powder  and  smearing  on  the  paste  is  obviously  the  orthodox  custom. 
As  an  ointment  should  be  perfectly  smooth  and  uniform,  especial 
care  was  taken  to  obtain  this  end;  and  for  this  purpose  advantage 
was  taken  of  the  solubility  of  chrysophanic  acid  in  hot  benzol, 
which  is  also  capable  of  dissolving  lard.  Two  drams  of  chryso- 
phanic acid  and  an  ounce  of  lard  were  dissolved  in  the  smallest 
necessary  quantity  of  boiling  benzol,  applying  heat  by  a  water  bath. 
Then  as  the  brown  solution  cooled  (the  vessel  containing  it  being 
placed  in  cold  water),  and  the  chrysophanic  acid,  much  less  soluble 
in  cold  than  in  hot  benzol  (Atffield),  became  rapidly  deposited,  the 
mixture  was  bri.skly  stirred  in  an  evaporating  basin.  As  the  mixture 
speedily  became  "  set,"  a  most  perfect  ointment  was  produced  in  a 
very  ready  manner.  After  leaving  the  ointment  spread  about  the 
dish  for  a  short  time,  the  benzol  almost  completely  evapoi'ated  from 
it,  leaving  it  quite  hard,  and  giving  it  the  appearance  of  being  stained , 
or  some  sort  of  soft,  yellowish  wax.  The  smell  of  benzol  adheres  to 
the  ointment  for  some  time,  but  finally  is  lost,  or  may  be  concealed 
by  some  essential  oil. 

The  writer  finds  that  the  properties  of  chrysophanic  acid  are  by 
no  means  confined  to  its  being  a  remedy  for  ringworm,  but  that  it 
is  likely  to  prove  a  valuable  addition  to  the  list  of  drugs  as  a  remedy 
for  other  non-parasitic  skin  diseases.  He  has  obtained  unquestion- 
ably good  results  with  it  in  the  treatment  of  psoriasis,  and  it  is  a 


250  YEA.R-BOOK    OF    PHARMACT. 

serviceable  application  in  cases  of  lupus.  He  adds  that  particular 
cai'e  must  be  taken  in  the  preparation  of  the  ointment  if  it  is  to 
turn  out  such  as  described  above.  In  the  first  place  the  acid  must 
be  thoroughly  dissolved  in  the  hot  benzol,  and  in  the  next  place, 
the  cooling  and  evaporation  of  the  benzol  must  be  conducted  as 
rapidly  as  possible.  With  this  view  the  process  of  dissolving  may 
be  conducted  in  a  small  glass  beaker,  placed  in  a  vpater  bath,  and 
when  solution  of  the  acid  and  the  lard  has  been  perfectly  accom- 
plished, the  solution  should  be  promptly  turned  into  a  cold  evapo- 
rating dish,  placed  in  cold  water,  and  immediately  briskly  stirred 
with  a  glass  rod  until  the  solution  has  become  fully  and  firmly 
"  set." 

In  a  subsequent  number  of  the  same  journal  we  find  a  communi- 
cation by  Dr.  H.  R.  Crocker,  who  states  that  he  used  chrysophanic 
acid  ointment  some  nine  months  previously  in  the  treatment  of  ring- 
worm. The  acid  was  prepared  by  Mr.  A.  W.  Gerrard,  and  "was 
employed  in  the  form  of  a  concentrated  solution  in  benzol,  which 
retains  about  tea  grains  to  the  fluid  ounce  when  cold,  as  well  as  in 
the  form  of  ointment,  made  with  ten  to  forty  grains  of  the  acid  to 
the  ounce  of  lard.  The  results  of  his  experiments,  which  were 
limited  to  parasitic  diseases,  led  him  to  consider  chrysophanic  acid 
as  by  no  means  deserving  of  unqualified  praise.  Mr.  Grerrard,  in 
the  same  paper,  adds  the  statement  that  vaseline  is  a  much  better 
solvent  of  the  acid  than  ordinary  fats,  and  that  the  use  of  benzol 
in  the  pi-eparation  of  the  ointment  is  not  at  all  necessary.  Hot  fats 
or  oils,  indeed,  appear  to  dissolve  chrysophanic  acid  in  almost  all 
proportions  ;  but  on  cooling,  a  good  deal  of  it  separates  again,  and  it 
is  necessary  to  rub  it  assiduously  during  the  cooling  in  order  to 
obtain  a  smooth  mass.  Mr.  A.  W.  Postans  recommends  tlie  addi- 
tion of  a  few  drops  of  otto  of  roses  to  disfjuise  the  peculiar  odour, 
and  also  states  that  Dr.  Ashburton  Thompson  has  pushed  the 
matter  even  further,  by  administering  goa  powder  and  chryso- 
plianic  acid  to  his  patients  internally  as  well  as  externally. 

The  botanic  source  of  goa  powder  is  expected,  according  to  Mr. 
Postans,  to  be  determined  by  means  of  a  specimen  plant,  growing 
at  present  in  the  Royal  Botanic  Gardens,  Edinburgh,  and  supposed 
to  be  the  source  of  the  drug. 

Glycerols  of  Phosphorus.  C.  Meniere.  (BSpert.  de  Pharm.,  1877, 
35-1;.)  In  preparing  this  glycerole  in  the  usual  way,  by  dissolving 
phosphorus  in  heated  glycerin,  a  poi-tion  of  the  phosphorus  not  un- 
frequently  separates  on  cooling,  giving  rise  to  an  opalescence  and 
subsequently  to  a  deposit.     This,  according   to  the  author,  may  be 


PHARMACY. 


251 


prevented  bj  'employing  phosphorus  in  a  finely  divided  condition, 
such  as  is  obtained  by  mixing  it  with  sugar  or  gum  arabic,  either 
of  which  is  soluble  in  glycerin.  The  powdered  sugar  or  gum  is 
mixed  with  a  small  quantity  of  glycerin,  so  as  to  yield  a  mixture 
of  the  consistence  of  honey.  This  is  heated  on  a  water  bath,  the 
phosphorus  incorporated  with  it,  and  the  remainder  of  the  glycerin 
then  added  in  small  quantities  at  a  time,  care  being  taken  that  the 
temperature  never  rises  above  50°  C. 

According  to  Reveil's  formula,  which  the  author  considers  the 
best,  the  preparation  should  contain  "10  gram  of  phosphorus  in  1000 
grams.  This  is  ten  times  weaker  than  the  preparation  made 
according  to  Dorvault's  formula ;  but  in  this  dilution  the  same  dose 
of  phosphoriis  is  much  more  readily  borne  by  the  stomach. 

Chloral  with  Solid  Fats.  (New  Remedies,  January,  1877.)  An 
anonymous  writer  in  the  Med.  and  Surg.  Bep.  says,  as  a  therapeutic 
agent,  chloral  has  become  so  popular  that  its  range  of  application  is 
as  diversified  as  any  drug  or  chemical  of  a  century's  standing ;  but 
its  nature  has  not  been  suflficiently  studied  to  construct  formula? 
readily  that  furnish  preparations  easily  dispensed  and  always  praise- 
worthy. On  the  contrary,  formulae  are  written  which  furnish  not 
only  inelegant,  but  almost  incompatible  preparations.  A  case  in 
point  is  its  combination  with  solid  fats.  It  is  a  matter  oftentimes 
overlooked,  if  not  entirely  unknown,  that  chloral  hydrate  is  a  solvent 
for  fats ;  so  much  so  that  solid  fats  become  liquefied  by  contact. 
Hence  it  is  not  advisable  to  prescribe  chloral  with  lard,  simple 
ointment,  or  even  with  simple  cerate,  in  a  very  large  proportion. 
With  oleum  theobromae  it  forms  an  unctuous  mass,  which  furnishes 
a  very  creditable  preparation  dispensed  as  an  ointment ;  but  to  make 
from  this  combination  a  suppository,  is  almost  an  impossibility. 
Still  less  possible  is  it  to  make  a  suppository  containing  with  chloral 
one  of  the  solid  extracts  which  must  previously  be  moistened  with  a 
little  water  to  make  it  miscible  with  the  soKd  fat,  as  a  drop  of  water 
increases  enormously  the  fluidity  of  the  oleaginous  mixture.  The 
writer  has  made  a  number  of  experiments  as  to  the  best  excipients, 
and  finds  that  equal  parts  of  spermaceti  and  oleum  theobromee 
have  the  advantage  over  any  other.  In  a  suppository  containing 
ten  to  twelve  grains  of  chloral  this  is  about  the  proper  proportion. 
Deviating  from  this  strength,  the  proportion  of  spermaceti  must  be 
increased  or  diminished  accordingly.  Vaseline  and  paraffin,  using 
three  of  the  former  to  two  of  the  latter,  make  a  very  good  base,  but 
it  does  not  melt  as  nicely  into  an  unctuous  mass  as  does  the  former. 

Phosphorus  Pills.     E.  J.  Appleby.      (Pharm.  Joiorn.,  3rd  series, 


0X0 


YEAR-BOOK    OF    PHARMACY. 


vii.,  289.)  The  author  has  tried  cacao  butter,  balsam  of  tolu,  and 
commou  resin  as  excipients  for  phosphorus,  and  finds  that  with  the 
first  named  the  mass  requires  some  time  and  patience  to  prepare, 
and  must  be  divided  into  pills  and  coated  at  once.  The  phosphor- 
ized  tolu  balsam  is  difficult  to  incorporate  with  other  ingredients, 
and  pills  made  from  it  soon  lose  their  shape,  and  are  with  difficulty 
soluble  in  water.  Phosphorized  resiu,  on  the  contrary,  is  easily  pre- 
pared, and  may  be  kept  under  water  for  any  length  of  time.  It  can  be 
quickly  reduced  to  a  fine  powder,  and  easily  made  into  a  pill  mass. 

Pills  properly  prepared  with  the  resin  are  thoroughly  disintegrated 
by  cold  water  in  a  very  short  time.  As  a  very  small  portion  only  of 
the  resin  is  required  for  an  ordinary  dose  of  phosphorus,  other  in- 
gredients may  be  combined  with  it  without  making  too  large  a  pill. 

Detection  of  Adulteration  in  Oleum  Theobromse.  G.  Ramsper- 
ger.  (Proc.  Amer.  Pharm.  Assoc,  187G.)  Of  all  tests  used  by  the 
author,  ether  was  found  to  be  the  best.  It  indicated  all  admixtures 
which  he  had  made  to  the  cacao  butter  (with  the  exception  of  ox- 
marrow)  either  directly  by  the  turbidity  of  the  solution  of  one  part  of 
the  adulterated  cacao  butter  in  two  parts  of  the  ether  (as  is  the  case 
with  the  adulterations  by  tallow,  beeswax,  and  barberry  wax,  and 
paraffin)  ;  or  if  not  immediately  after  solution,  then  by  becoming 
turbid  after  standing  for  some  time,  and  by  forming  little  crystals 
and  gi'ains  by  spontaneous  evaporation  of  the  solution,  which  crystals 
are  not  soluble  again  in  two  parts  of  ether  at  common  temperature 
(this  is  the  case  with  Japan  wax  and  spermaceti,  with  or  without 
the  addition  of  ox-marrow).  Anilin  .shows  adulterations  with  tallow 
and  wax  almost  as  well  as  ether.  Other  solvents  of  cacao  butter 
cannot  be  used  as  tests ;  all  the  difierent  fats  and  wax  being  easily 
soluble  in  them,  with  the  exception  of  barben*y  wax,  which  makes  a 
clear  solution  only  with  chloroform. 

Next  to  ether  and  aniline  the  taste  seems  to  be  the  most  reliable 
test.  The  droppings  on  hot  iron,  or  burning  the  mixtures  with 
wicks,  does  not  show  plainly  enough  an  adulteration  with  25  per 
cent,  of  tallow  ;  and  of  freshly  rendered  beef  tallow,  even  50  per 
cent,  could  be  hardly  recognised.  With  Klencke's  test  the  author 
did  not  succeed ;  he  was  very  seldom  able  to  see  any  difference  in 
the  shape  of  the  drops  of  cacao  butter  from  that  of  tallow  or  ox- 
marrow  drops  on  water;  the  former  expanding  dish-like  over  the 
surface  of  the  warm  water  about  as  much  as  the  latter. 

The  specific  gravity  is  unreliable.  The  same  seems  to  be  the  ca.se 
with  the  point  of  fusibility  as  a  test ;  at  least  he  found  that  recently- 
melted  and  re-congealed  cacao  butter  melts  at  a  temj)erature  several 


PHARMACY. 


253 


degrees  lower  than  such  as  had  been  melted  several  weeks  before. 
This  may  account  for  the  conflicting  statements  about  this  point. 
Guided  by  the  result  of  the  experiments  made,  the  author  examined 
a  dozen  specimens  of  oleum  theobromse  which  he  had  collected  ia 
different  wholesale  and  retail  stores.     The  result  was  as  follows  : — 


No. 


3 
4 
5 
6 
7 
8 
9 

10 
11 
12 


Specific 

Melting 

Gravity. 

Point. 

0-850 

31°  C. 

0-897 

33°  C. 

0-900 

31°  C. 

0-874 

30°  C. 

0-976 

34°  C. 

0-938 

32°  C. 

0-979 

34°  C. 

0-875 

34°  C. 

0-978 

30°  C. 

0-872 

35°  C. 

0-919 

33"  C. 

0-959 

30°  C. 

Solution  in  Ether  or 
Anilin. 


Pure 
Pure 

A  little  rancid 

Pure 

Not  quite  pure 

Pure 

Very  little  rancid 

Strongly  raucid 

Pure 

Pure 

Pure 

Eancid 


Clear 

Clear 

Clear 

Clear 

Turbid 

Clear 

Clear 

Very  turbid 

Clear 

Very  little  turbid 

Clear 

Clear 


This  shows  two  or  three  adulterations  among  the  dozen,  one  of 
them  with  tallow  plainly  recognisable. 

A  New  Mode  of  making  Grey  Powder.  A.  Bottle.  (Pharm. 
Journ.,  3rd  series,  vii.,  4G9.)  The  author  discusses  the  question 
whether  grey  jDowder  depends  for  its  efficacy  on  the  impalpably 
minute  division  of  the  mercury,  or  on  the  presence  of  oxides,  and 
arrives  at  the  conclusion  that  the  use  of  a  powder  containing  mercury 
in  the  higher  state  of  oxidation  ought  to  be  avoided,  and  that  it  is 
desirable  to  have  Hyd.  c.  Greta,  prepared  at  intervals  not  too  far  apart. 
He  suggests  a  slight  deviation  from  the  British  Pharmacopoeia 
process,  to  the  extent  of  substituting  for  the  slow  process  of  tritura- 
tion in  a  porcelain  mortar,  active  agitation  in  a  wide-mouthed  glass 
bottle,  by  which  means  the  B.  P.  may  be  prepared  and  the  metal 
minutely  sub-divided  with  an  expenditure  of  very  little,  if  any, 
more  time  and  labour  than  is  required  to  be  devoted  to  the  prepara- 
tion of  a  tincture. 

The  Use  of  Petroleum  Benzin  in  Pharmacy.  L.  Wolff.  {Amer. 
Journ.  Pharm.,  January,  1877,  1.)  Petroleum  benziu  has  been  fre- 
quently proposed  and  variously  experimented  with  by  different 
operators,  with  the  view  of  its  substitution  for  the  much  higher  priced 
ether  in  preparing  oleo  resins,  and  has  been  repeatedly  found  not  to 
answer  the  purpose  intended  for  it.  Although  its  valuable  solvent 
powers  for  fatty  matter,  wax,  and  essential  oils  cannot  be  disputed. 


254  YEAR-BOOK    OF    PHARMACY. 

it  fails  to  extract  the  resins  and  the  active  ingredients,  which  are 
of  the  utmost  importance  in  oleo  resins.  Ginger  treated  with  benzin 
yields  an  oil  containing  all  the  odoriferous  properties  thereof,  but 
extracting  none  of  the  pungent  tasting  resin  for  the  remedial  pro- 
perties of  which  it  is  justly  celebrated,  and  which  subsequent  to  the 
benzin  process  is  readily  dissolved  from  it  by  etlier  or  alcohol. 
Buchu  under  a  like  treatment,  as  reported  by  another  contributor 
of  this  journal  on  this  subject,  gives  an  oily  substance  devoid  of  the 
diuretic  propei'ties  of  the  leaves,  though  possessing  their  speciBc 
odour.  Cubebs,  though  completely  exhausted  by  it  of  its  fixed  and 
essential  oils,  fails  to  yield  its  cubebic  acid  to  it;  black  pepper 
its  piperin  ;  and  wormseed  its  resin  and  santonin.  But  all  the  sub- 
stances mentioned,  and  many  more  which  have  been  subjected  to  the 
same  process,  are  readily  deprived  of  their  fixed  and  essential  oils, 
leaving  them  inodorous,  seemingly  dry  and  incoherent  powders, 
that  are,  if  treated  with  alcohol,  ether,  or  chloroform,  readily  de- 
pi'ived  of  their  resins,  thus  affording  a  method  for  obtaining  them 
separate  from  wax,  fixed,  and  essential  oils. 

Its  extraordinary  solvency  for  essential  oils  destines  benzin  for 
an  important  place  in  pharmacy ;  and  oils  derived  by  its  aid  from 
cinnamon,  cloves,  and  other  drugs  are,  if  theii'  odour  is  any  indica- 
tion of  their  value,  if  not  superior,  certainly  not  inferior,  to  the 
distilled  oils  of  these  articles. 

The  oils  obtained  by  exhaustion  with  benzin  and  its  subsequent 
evaporation  are  mixed  with  wax  and  fixed  oils  to  some  extent,  which 
can  easily  be  separated  therefrom  by  dissolving  in  alcohol,  in  wbich 
the  latter  are  insoluble,  filtration  of  this  solution,  and  either  expul- 
sion of  the  alcohol  by  evaporation  at  the  moderate  heat  of  a  water 
bath  or,  much  safer  and  better,  by  mixing  the  filtered  alcoholic  solu- 
tion with  several  times  its  bulk  of  water,  when  the  essential  oil  will 
rise  to  the  surface  or  subside  beneath  it,  as  its  specific  gravity  may  be. 

The  oils  by  this  cold  process  have  a  beautiful  aroma,  superior  to 
many  of  the  distilled  ones;  and  the  easy  manner  of  obtaining  them 
may,  without  doubt,  prove  a  valuable  method  for  the  pharmacist, 
who  cannot  always  procure  in  the  market  tlie  oils  he  wants,  and 
has  no  facilities  for  distilling  them,  besides  giving  him  fair  means 
to  arrive  at  a  quantitative  estimate  of  the  essential  oil  contained  in 
an  article  under  analysis. 

The  es.sential  oil  of  parsley  seed  cannot  thus  be  separately  pre- 
pared by  the  aid  of  benzin,  as  it  contains  another  peculiar  oily 
substance,  well  known  by  the  name  of  "  apiol,"  which  is  soluble  both 
in  benzin  and  in  alcohol. 


PHAEMACT.  255 

A  great  deal  of  the  apiol  in  the  market,  both  in  bulk  and  in  cap- 
sules, is  nothing  more  than  an  oleo  resin  of  parsley  seed,  which  can 
lay  no  claim  -whatever  to  its  name,  being  of  green  colour,  insoluble 
to  a  large  extent  in  alcohol,  and  congealing  at  ordinaiy  winter  tem- 
perature ;  all  of  which  properties  "  true  apiol "  does  not  possess. 
Apiol  has  come  into  extensive  use  of  late  years,  secured  high  praise 
as  an  emmenagogue,  and  is  also  claimed  by  its  discoverers  to  be  an 
antiperiodic  but  little,  if  any,  inferior  to  quinia;  but  its  high  price, 
due  to  the  expensive  process  as  proposed  by  Messrs.  Loret  & 
Homelle,  perhaps  more  than  anything  else,  prevents  its  general 
introduction. 

Powdered  parsley  seed,  exhausted  with  benzin,  and  the  liquid 
spontaneously  evaporated,  yields  a  mixture  containing  principally 
fixed  oil,  wax,  and  apiol ;  the  latter,  alone,  being  sohible  in  alco- 
hol, can  readily  be  recovered  therefrom  by  repeated  washings  in 
stronger  alcohol.  The  washings,  evaporated  over  the  water  bath 
with  a  gentle  heat,  leave  as  residue  "  true  apiol,"  corresponding  in 
every  respect  with  the  article  sold  under  the  name  of  "  Joret  & 
Momolle's,"  having  the  advantage  of  its  low  price  making  it  acces- 
sible to  persons  of  limited  means  as  well  as  to  the  more  favoured 
by  fortune,  especially  if  it  is  not  dispensed  in  capsules,  for  which 
there  is  no  occasion,  since  it  may  be  given  dissolved  in  essence  of 
peppermint,  or  in  emulsion,  disguised  by  the  oil  of  the  same  name. 
Samples  of  "  apiol "  prepared  in  this  manner  have  been  tried  by 
several  prominent  physicians  in  their  practice,  and  were  pro- 
nounced to  be  equally  as  efficient  as  the  imported  French  article. 
Quite  frequently  the  fixed  oils  much  encumber  the  result  of  phar- 
maceutical operations,  as  is  prominently  the  case  in  preparing  the 
"Alcoholic  Extract  of  ISTux  Vomica,"  which  has  often  been  noticed 
and  given  attention  to  by  many  writers.  (See  American  Journ. 
Pharm.,  1874,  p.  405;  also.  Professor  Procter  on  the  same.)  Nux 
vomica,  if  exhaiisted  with  benzin,  yields  a  large  percentage  of  a 
clear  fixed  oil,  congealing  at  ordinary  winter  temperature ;  and  the 
powder,  if  subsequently  treated  in  the  usual  manner  with  stronger 
alcohol,  gives  an  extract  which  offers  no  trouble  by  proper  evapora- 
tion in  reducing  it  to  the  dry  state.  The  oil  derived  from  the 
benzin  exhaust,  to  make  sure  of  not  losing  any  strychnia  or  brucia 
that  may  be  contained  therein,  should  be  repeatedly  shaken  with 
dilute  alcohol  until  the  washings  fail  to  betray  to  the  palate  the 
specific  bitter  taste  of  their  alkaloids ;  then  the  washings  must  be 
mixed  with  the  extract  in  course  of  evaporation,  and  the  whole  re- 
duced to  proper  consistency.     By  the  ordinary  way,  the  separation 


256 


YEAR-BOOK    OF    PHARMACY. 


of  the  oil  from  the  extract  is  at  best  a  tedious  matter,  causing  the 
loss  of  extract,  and  is  never  completely  performed,  thus  ju'eventing 
evaporation  to  dryness,  which  by  the  beuzin  process  is  readily 
effected. 

Another  article,  which  the  pharmacist  has  frequently  to  pui'chase 
at  an  exorbitant  price,  is  "purified  oleic  acid,"  which  has  been 
much  used  of  late  iu  making  the  oleates  now  in  ixse,  and  can  be 
easily  and  at  small  expense  prepared,  with  benzin  as  solvent,  in  the 
following  way : — 

Oil  of  sweet  almonds,  saponified  with  caustic  potash  and  the  soap 
decomposed  with  tartaric  acid,  is  washed  with  hot  water  to  separate 
the  precipitated  bitartrate  of  potassium  from  the  mixture  of  oleic 
and  palmitic  acids.  These  are  combined  with  litharge,  forming  the 
oleo-margarate  of  lead,  from  which  the  benzin  dissolves  the  oleate 
of  lead,  leaving  as  residue  the  undissolved  palmitate  thereof.  From 
the  benzin  solution  the  lead  is  precipitated  by  dilute  hydrochloric 
acid  in  form  of  chloride  of  lead  ;  and  on  evaporation  of  the  benzin, 
"oleic  acid"  will  remain,  sufficiently  pure  for  pharmaceutical 
purposes,  giving  clear  and  permanent  solutions  with  the  red  and 
yellow  mercurial  oxides,  as  high  as  thirty  per  cent,  if  necessary. 

As  crude  commercial  oleic  acid  can  be  bought  at  very  low  figures, 
it  may  be  purified  by  combining  it  with  litharge,  deriving  from  it 
the  oleate  of  lead,  from  which  again,  by  the  aid  of  benzin,  the  puri- 
fied oleate  can  be  separated,  and  as  before  stated,  purified  oleic  acid 
prepared  at  but  a  small  expense. 

To  gain  the  same  end,  the  simplest  way  perhaps  is  to  utilize  the 
ready-made  oleo-palmitate  of  lead,  the  officinal  lead  plaster,  dissolve 
it  in  benzin,  and  extract  from  it  the  oleic  acid  by  precipitating  the 
lead  by  aid  of  hydrochloric  acid. 

Oleic  acid  thus  prepared  has  been  used  for  some  time,  and  found 
to  answer  better  for  the  preparation  of  the  oleates  than  the  article 
sold  by  some  of  the  manufacturing  chemists. 

The  above  results  by  no  means  limit  the  utility  of  petroleum 
benzin  as  a  solvent  and  important  pharmaceutical  factor ;  but  they 
will  show  that  this  refuse  article,  of  comparative  little  commercial 
value,  which  has  been  applied  to  but  little  more  than  the  removal 
of  oil,  grease,  or  paint  stains,  may  be  turned  to  good  account  by  its 
very  deficiency  to  act  like  ether  or  similar  substances  as  a  general 
solvent  for  both  fats  and  resins. 

The  Union  of  Chloral  Hydrate  and  Camphor.  E.  C.  Saunders. 
{Pharm.  Juurn.,  3rd  series,  vii.,  89.)  Tiie  author  quotes  a  number 
of  experiments,  the  results  of  which  indicate  that  no  chemical  action 


PHARMACY.  257 

takes  place  wlien  chloral  hydrate  and  camphor  are  mixed  in  the 
cold.  Both  are  volatile  at  ordinary  temperatures;  and  the  follow, 
ing  experiment,  which  was  performed  to  ascertain  which  was  the 
solvent,  conclusively  proves  that  it  is  the  vapours  which  act  upon 
each  other.  Two  lumjis,  one  of  chloral  hydrate  and  one  of  camphor, 
were  placed  about  an  inch  apart  on  a  porcelain  plate,  and  covered 
with  a  bell  glass.  In  fifteen  minutes  the  surface  of  the  camphor 
was  quite  damp,  but  the  chloral  was  quite  dry.  In  three  houi-s  the 
chloral  was  still  dry,  while  the  camphor  was  quite  wet  and  standing 
in  the  midst  of  liquid.  In  twelve  hours  the  liquid  had  reached  the 
chloral,  the  upper  surface  of  which  was  still  dry,  while  in  twenty 
hours  both  lumps  were  half  liquefied,  and  the  inner  surface  of  the 
bell  glass  was  covered  with  moisture.  This  would  almost  seem  to 
point  out  that  the  vapour  of  the  chloral  was  the  solvent;  but  it  was 
found  while  one  part  of  camphor  would  form  a  permanent  liquid 
with  three  and  a  half  parts  of  chloral  hydrate,  one  part  of  chloral 
dissolved  by  the  aid  of  heat,  with  two  parts  of  camphor  solidified  to 
a  soft  crystalline  mass  when  cold,  from  the  camphor  crystallizing. 
It  is  most  probable  that  the  camphor  is  the  solvent,  which  would 
also  seem  likely,  as  camphor  is  an  essential  oil,  and  is  known  to 
render  other  bodies  fluid.  The  change  of  coloui',  with  the  formation 
of  an  oily  liquid,  would  seem  to  point  to  chemical  action  occurring 
when  the  mixture  is  subjected  to  sti'ong  heat. 

The  following  notes  of  the  solubility  of  the  mixture  in  various 
fluids  may  be  serviceable  to  any  who  are  called  upon  to  dispense 
it,  or  to  physicians  who  feel  inclined  to  try  the  effects  of  it. 

It  is  miscible  in  all  proportions  with  alcohol,  sp.  gr.  '838,  bisul- 
phide of  carbon,  ether,  and  olive  oil.  It  is  soluble  in  eleven  parts 
of  alcohol,  sp.  gr.  '9S7.  It  is  insoluble  in  water.  It  forms  a  clear 
mixture  with  one  and  a  half  parts  of  chloroform,  but  a  further 
addition  of  three  parts  of  chloroform  renders  it  turbid.  Camphor 
forms  a  permanent  liquid  with  three  times  its  weight  of  chloral 
hydrate.  The  experiments  were  conducted  with  the  atmosphere  at 
a  temperature  of  about  80^;  the  fact  is  mentioned,  as  it  may  have 
influenced  the  solubility  slightly. 

Glycerole  of  Nitrate  of  Bismuth.  B.  Squire.  (Pharm.  Journ., 
3rd  series,  vii.,  389.)  Desiring  to  employ  a  solution  of  a  simple  bis- 
muth salt  in  certain  skin  diseases,  the  author  tried  glycerin  as 
a  solvent,  and  found  that  the  nitrate  was  freely  sohihle  in  glycerin, 
and  that  it  dissolved  without  decomposition.  This  solution  may 
even  be  diluted  with  water  without  depositing  any  more  than  a 
trifle  of  the  salt  for  nearly  an  hour. 

S 


258  YEAR-BOOK   OF   PHARMACY. 

With  the  view  of  studying  the  reactions  of  tliis  gljcerole, 
Mr.  John  "Williams  prepared  some  of  it  by  dissolving  20  per  cent,  of 
crystallized  nitrate  of  bismuth  in  Price's  glycerin  (Pliarm.  Joum., 
3rd  series,  vii.,  470).  He  found  the  solution  is  best  effected  in  the 
cold ;  if  much  heat  is  employed  in  the  preparation,  the  glycerole. 
■nhen  diluted  does  not  give  a  clear  solution  but  a  milky  one,  at  any 
rate  at  the  end  of  a  few  hours.  The  property  of  bearing  dilution 
■with  water  without  producing  a  turbid  solution,  appears  to  dimin- 
ish by  keeping.  The  diluted  solution  does  not  bear  boiling,  but 
when  so  treated  deposits  a  basic  salt  not  afterwards  soluble  in  water. 
Caustic  potash  (or  soda),  added  to  the  glycerole  diluted  with  water, 
first  causes  a  white  precipitate,  which  is,  however,  perfectly  soluble 
in  an  excess  of  the  alkali,  a  bright  clear  liquid  being  produced,  which 
is  perfectly  miscible  with  water  in  all  proportions,  and  might  pos- 
sibly be  employed  medicinally  as  a  substitute  for  the  liq.  hismnthi 
mnmonio-citratis  of  the  Pharmacopoeia.  From  this  reaction  Mr. 
Williams  is  inclined  to  infer  that  the  glycerole  is  not  a  mere  solu- 
tion of  the  nitrate  of  bismuth  in  glycerin,  but  is  a  chemical  com- 
bination ;  and  that  the  glycerin  is  playing  a  part  somewhat  similar 
to  that  taken  by  the  citric  acid  in  the  liquor  of  the  Pharmacopoeia. 
Ammonia,  however,  cannot  be  substituted  for  potash  in  this  re- 
action, no  excess  of  the  former  making  a  clear  solution,  although  a 
trace  of  bismuth  is  held  in  solution,  as  can  be  proved  by  adding 
sulphate  of  ammonium  to  the  filtrate. 

Mr.  Williams'  opinion  that  this  preparation  is  a  real  chemical 
combination  is  not  shared  by  Mr.  W.  Willmott,  who  regards  the 
difierence  between  the  behaviour  of  ammonia  and  potash  in  this 
reaction  as  an  indication  that  the  glycerin  here  merely  acts  as  a 
solvent,  but  does  not  form  a  chemical  compound  {Pharm.  Joum., 
3rd  series,  vii.,  830.)  The  same  writer  suggests  the  following  for- 
mula for  this  preparation : — 

Nitrate  of  Bismuth gss. 

Distilled  TVater 5ij. 

Price's  Glycerin ad  5VJ. 

Dissolve  the  nitrate  of  bismuth  in  two  fluid  drams  of  the  gly- 
cerin previously  mixed  with  the  distilled  water ;  then  add  the 
solution  to  the  remainder  of  the  glycerin,  and  mix  well  together. 

This  is  prepared  at  once  and  without  the  slightest  difficulty.  It 
contains  five  grains  of  the  active  ingredients  in  each  fluid  dram, 
and  is  most  convenient  for  prescribing.  Even  therapeutically  the 
addition  of  the  water  is  an  advantaee,  since,  as  in  the  cases  of  tan- 


PHARMACY.  259 

nin  and  borax,  the  density  of  the  undiluted  glycerin  prevents  the 
action  of  the  remedy  from  coming  readily  into  play.  It  is  better  in 
each  case  to  dilute  with  a  little  water  before  using. 

Administration  of  Oils  and  Oleo-Resins  by  means  of  Wafer  Cap- 
sules. S.  Limousin.  {Rapert.  cle  Pharm.,  1877,  257.)  The  author 
suggests  the  use  of  cachets  de  pain,  or  wafer  capsules,  as  vehicles  for 
administering  castor  oil,  cod  liver  oil,  copaiba,  and  other  liquids 
which  do  not  act  upon  the  substance  of  the  wafer.  The  two 
empty  halves  of  the  capsules  are  united  in  the  usual  manner,  except 
on  one  portion  of  the  rim,  thus  leaving  an  opening  through  which 
the  oil  is  introduced  by  means  of  a  pipette.  The  orifice  is  then 
closed  by  moistening  it.  The  oil  may  also  be  placed  in  the  cavity  of 
the  lower  wafer,  and  the  upper  one  rapidly  affixed  to  it  before  the  oil 
has  had  time  to  spread  to  the  margin.  Cod  liver  oil  communicates  its 
odour  to  the  capsule  unless  the  inner  surface  of  the  wafer  be  pre- 
viously covered  with  collodion. 

Canada  Balsam  as  an  Excipient  for  Pills.  M.  Daunecy.  (U  Union 
Pharmaceutique,  1877,  1G8.)  To  prevent  pills  from  becoming  hard 
and  insoluble,  the  author  suggests  a  mixture  of  one  part  of  wax 
and  three  parts  of  Canada  balsam.  This  mixture  possesses  the  pro- 
perty, even  if  added  in  small  proportion,  of  binding  together  the 
component  parts  of  pill  masses,  of  keeping  the  pills  jDermanently 
soft  and  yet  sufficiently  solid  to  prevent  them  from  flattening,  and 
of  preventing  deliquescent  constituents  from  attracting  moisture. 
He  has  prepared,  by  means  of  this  excipient,  pills  of  potassium 
acetate  containing  three  grains  of  the  latter  in  each  pill,  and  re- 
maining entirely  unaltered  on  keeping.  Pills  prepared  in  this  man- 
ner readily  disintegrate  in  the  stomach. 

Oleate  of  Bismuth.  S.  C.  Betty.  (Pharm.  Journ.,  3rd  series 
vii.,  469.)  Having  noted  the  power  of  oleic  acid  in  dissolving  oxide 
of  bismuth  to  a  considerable  extent,  the  author  suggests  the  follow- 
ing formula  for  such  a  combination  : — The  oxide  of  bismuth,  B.  P. 
(the  trisnitrate  and  carbonate  being  useless  for  this  purjjose),  is 
ground  very  fine,  and  the  oleic  acid  gradually  incorporated  with 
it.  The  mixture  being  placed  in  a  suitable  vessel  is  subjected  to  a 
temperature  of  nearly  its  boiling  point;  then  allowed  to  digest,  wdth 
frequent  agitation,  at  a  temperature  of  about  60°  during  four  days, 
or  until  it  solidifies.  The  result  is  pharmaceutically  a  plaster  ; 
chemically,  an  oloate  of  bismuth,  containing  20  per  cent,  of  the 
base.  Respecting-  its  utility  as  an  endermic  application,  it  is  stated 
that  the  preparation  melts  readily  in  contact  with  the  skin,  is  bland 
to  an  excoriated  surface,  and  penetrating  by  its  limpidity. 


260  YEAR-BOOK    OP    PHARMACY. 

Ferric  Citrophosphate.  R.  Rother.  (Fharmacisf,  Sept.,  187G.) 
Citric  acid  is  one  of  the  most  remarkable  of  the  oreranic  acids.  Its 
constitution  is  so  peculiar  and  unintelligible  that;  synthetic  chem- 
istry has  failed  to  produce  it ;  neither  has  any  process  of  disruption 
yielded  it  from  more  complicated  compounds.  It  is,  in  our  present 
knowledge  of  the  substance,  most  emphatically  an  organic  acid.  Ifi 
is,  however,  a  noticeable  fact  that,  considering  the  interest  and  im- 
portance attaching  to  the  citrates  as  a  class,  they  have  been  but  im- 
perfectly studied.  The  marvellous  property  possessed  by  citric  acid 
of  rendering  metallic  bases  insusceptible  to  many  of  the  ordinary 
reagents  has  long  been  known.  This  action  has  been  interpreted  in 
various  ways,  and  given  rise  to  some  of  the  most  striking  theoretical 
speculations.  From  the  time  that  H.  Rose  first  observed  the  ready 
solubility  of  dry  ferric  citrate  in  pi'esence  of  normal  monad  citrates 
to  the  pi'csent,  no  definite  and  reliable  knowledge  existed  in  regard 
to  the  constitution  of  these  compounds.  The  opinion  largely  pre- 
vailed that  they  were  but  mechanical  mixtures ;  that  is,  mere  solu- 
tions of  one  salt  in  the  other,  without  reference  to  equivalency.  The 
first  step  in  the  direction  of  a  comprehensive  view  of  this  heretofore 
hopelessly  intricate  subject  was  made  by  the  writer  (Laboratory, 
Feb.,  1876),  in  showing  that  ferric  salts  with  monobasic  radicals 
formed,  by  a  combination  of  double  decomposition  and  additive 
affinity,  a  peculiar  green  double  citrate  of  iron  and  the  monad 
metal,  whilst  the  monobasic  or  dibasic  radical  passed  to  the  base  of 
the  citrate  actually  decomposed.  By  means  of  dialytic  experiments 
(Ame^-ican  Journal  of  Pharmacy,  April,  1876)  the  writer  added 
further  proof  in  confirmation  of  this  result,  but  also  showed  that 
in  case  of  the  citrophosphoric  compounds  a  rearrangement  of  more 
complicated  character  takes  place. 

All  compound  salts  may  be  divided  into  two  classes.  Double, 
triple,  and  quadruple  salts  are  formed  from  dibasic,  tribasic,  and 
tetrabasic  acids  when  each  iodividual  unit  of  equivalency  is  satura- 
ted by  a  distinct  basic  radical.  Secondary,  tertiary,  and  quaternary 
salts  are  produced  when  each  independent  unit  equivalency  of  a 
polyatomic  metal  is  saturated  by  distinct  acid  radicals  of  corres- 
ponding basicity. 

The  writer's  process  for  preparing  aramonio-ferric  citrophosphate 
(Pharmacist,  August,  1871)  indicates  that  two  equivalents  of  ferric 
orthopho.sphate  and  one  equivalent  of  triamraonic  citrate  react  upon 
each  other  in  the  production  of  a  soluble  amorphous  compound 
readily  obtainable  in  splendid  brown-green  scales.  The  solution, 
when  subject  to  dialysis,  gave  no  evidence  of  dissociation,  showing 


PHARMACr.  261 

that  no  crysiallizable  salt  is  present.  The  formation  of  the  com- 
pound, therefore,  determines  a  basic  condition  made  apparent  by 
the  presence  of  ferric  oxjcitrate  or  free  ferric  hydrate  (^Pharmacist, 
May,  1876).     Its  generation  may  then  be  represented  as  follows  :  — 

4  (Fe  P  0,)  +  2  (N  H,)3  C^  H,  O7  +  3  (0  H.)  =  Fe  C^  H.^  0,  (N  H,)  + 
C,  H,  O7.  Fe  (0  H)3  +  2  (Fe  P  0,).  (N  H,)3  H3  (P  O,)^. 

As  this  reaction  assumes  the  production  of  an  ammonio-ferric 
phosphate  in  which  one  equivalent  each  of  monammonic  and  diam- 
monic  phosphate  are  seemingly  united,  the  writer  endeavoured  to 
produce  this  double  phosphate  independent  of  the  citrate  by  dissolv- 
ing freshly  precipitated  ferric  phosphate  in  a  mixture  of  the  two 
ammonium  phosphates,  bat  no  solution  appeared  to  take  place. 
Ferric  citrate  was  then  substituted  for  the  ammonium  phosphates, 
when  rapid  solution  was  effected,  thus  enabling  the  writer  to  add 
one  more  interesting  iron  salt  to  the  list  of  those  already  discovered 
by  him.  The  ferric  citropliosphate  obtained  by  this  combination  is 
a  secondary  anhydrous  salt,  having  the  composition  Fco  (P  O4) 
(CgHjOy),  and  easily  obtainable  in  beautiful  brown-green  scales. 
It  forms  in  long  slender  blades,  a  shape  characteristic  of  feme 
citrate.  In  concentrated  solution  it  is  absolutely  permanent,  show- 
ing also,  in  this  resp3ct,  one  of  the  properties  of  ferric  citrate.  It 
has  a  sweet,  acidulous  taste,  free  from  metallic  flavour  and  the 
saline  nauseousness  of  some  of  the  ferric  double  citrates  now  in  use. 
There  can  be  no  doubt  of  its  complete  superiority  over  all  other 
citroferric  phosphates  at  present  so  largely  employed,  either  in  a 
pharmacal  or  therapeutic  aspect.  On  the  assumption  that  tliis  salt 
is  one  of  the  components  of  the  ammonio-ferric  citrophosphate  above 
described,  the  formation  may  be  written  as  follows : — 

2(FePO,)-i-(NH,)3C6H5  07^ 

Feo(P0,)(C,H,0,)  +  (NHj3P0,. 

This  result  seems  quite  probable,  since,  as  the  basicity  of  the  acids 
is  apparently  alike,  a  possibility  of  closer  union  is  not  precluded, 
and  hence  we  may  have  the  actual  combination  of  the  two  constitu- 
ents in  the  condition  of  a  secondary  double  salt. 

It  is  a  remarkable  fact,  worthy  of  note  in  this  connection,  that 
ferric  pyrophosphate  is  practically  insoluble  in  ferric  citrate.  This 
property,  therefore,  supports  the  writer's  constitutional  formula  of 
the  officinal  pyrophosphate,  making  it  a  mixture  of  ammonio-ferric 
pyrophosphate,  ammonio-ferric  citrate,  and  free  ferric  citrate. 

As  previously   suggested   by  the   writer    {American   Journal  of 


262  YEAR-BOOK    OF    PHARMACY. 

Pliarmacij,  April,  187G),  it  was  found  that  the  most  practical  and 
expeditious  process  of  preparing  the  ferric  citrophosphate  consisted 
in  precipitating  the  iron  as  a  mixed  phosphate  and  oxycarbonate, 
and  dissolving  the  mixture  in  citric  acid.  Ferric  oxycarbonate 
(Pharmacist,  Dec,  1873)  is  so  incomparably  superior  in  every  re- 
spect to  the  ordinary  ferric  hydrate  that  no  operator  who  has  once 
employed  it  will  ever  abandon  its  use.  The  compact  ferric  phos- 
phate (Pharmacist,  Dec,  1873,)  is  equally  an  improvement  on  the 
gelatinous  kind.  In  the  production  of  ferric  citrophosphate  the 
writer  combined  the  processes  of  the  two  iron  salts  as  follows  : — 


Solution  of  Ferric  Sulphate 

one  pint. 

Disodic  Orthophosphate,  Cryst.     . 

7  troy  ozs. 

Disodic  Carbonate,  Cryst. 

9     „      „ 

Citric  Acid,  Cryst. 

3     „      „ 

Water 

sufficient. 

Add  the  sodic  phosphate  to  the  solution  of  ferric  sulphate,  and 
apply  heat  until  solution  is  effected  ;  now  place  the  sodic  carbonate 
into  a  capacious  vessel,  pour  on  half  a  pint  of  water,  and  apply  heat 
until  the  salt  has  dissolved  ;  then  add  in  rapid  succession  the  former 
solution,  one-fourth  at  a  time,  and  maintain  the  heat,  with  constant 
stirring,  until  effervescence  has  ceased ;  dilute  the  mixture  with 
water  to  the  measure  of  eight  pints,  and  when  the  precipitate  has 
perfectly  subsided  decant  the  supernatant  liquid,  and  mix  the 
sediment  again  with  a  fresh  portion  of  water,  as  before ;  after  three 
or  four  washings  in  this  manner,  pour  the  precipitate  upon  a  muslin 
strainer  and  press  it  thoroughly ;  place  the  residue  in  a  porcelain 
capsule,  add  the  citric  acid  and  apply  a  water  bath  heat  until  per- 
fect solution  has  occurred  ;  finally,  pour  the  liquid  upon  plates  of 
glass  or  porcelain,  and  expose  it  in  the  open  air  to  dry.  The  yield 
is  about  6|  troy  ounces. 

In  this  formula  a  slight  excess  of  sodic  phosphate  is  employed, 
since  the  sodium  carbonate  has  a  tendency  to  take  away  the  acid  of 
the  ferric  phosphate.  Hence,  the  two  precipitates  may  also  be  pre- 
pared separately,  mixed  after  washing,  and  dissolved  as  above. 
With  the  adjusted  quantity  of  sodium  phosphate,  as  directed  in  the 
above  formula,  the  final  result,  however,  agrees  very  closely  with 
the  theoretical  yield. 

If  desirable,  the  salt  may  be  retained  in  solution,  which,  if 
sufficiently  concentrated,  will  remain  absolutely  permanent.  A 
solution  containing  one-half  a  troy  ounce  of  the  salt  iu  the  fluid 
ounce  appears  to  be  the  most  convenient  form. 

This  salt,  similar  to  the  officinal  pyrophosphate,  when  mixed  with 


PHARMACY.  263 

any  acid  stronger  than  the  citric,  is  completely  decomposed,  ferric 
phosphate  being  precipitated.  The  officinal  pyrophosphate,  when 
mixed  with  orthophosphoric,  pyrophosphoric,  metaphosphoric, 
chlorhydric,  nitric  or  sulphuric  acid,  is  instantly  precipitated. 

The  white  gelatinous  precipitate  is  insoluble  in  either  of  the  phos- 
phoric acids,  but  any  of  the  latter  three  acids,  when  in  sufficient 
excess,  again  dissolve  it.  The  erroneous  belief  is  still  abroad  that 
the  officinal  pyrophosphate  of  iron  should  form  a  clear  solution 
when  mixed  with  diluted  phosphoric  acid.  It  is,  however,  about 
time  now  that  it  was  generally  understood  that  any  citrophosphoric 
compound  is  incompatible  with  free  orthophosphoric  acid,  by  reason 
of  the  fact  that  any  citrate  present  will  be  decompossd,  its  acid 
being  liberated ;  and  as  free  citric  acid  fails  to  dissolve  the  various 
ferric  phosphates,  these  must  of  necessity  be  thrown  out  of  solu- 
tion. 

Pepsin  combined  with  Glycerin.  M.  C  a  til  Ion.  (BepSrt.  de 
Pharm.,  1877,  No.  11.)  Glycerin  is  recommended  by  the  author 
both  for  the  extraction  of  pepsin  and  for  its  medicinal  exhibition. 
Administered  in  this  form,  the  pepsin  is  reported  to  exercise  an 
increased  digestive  power,  while  another  advantage  is  to  be  found 
in  the  fact  that  a  solution  of  pepsin  in  glycerin  may  be  kept  for  a 
great  length  of  time  without  suffering  any  change. 

The  Spectroscope  in  Pharmacy.  W.  Gilmour.  (Pharm.  Jouni., 
3rd  series,  vii.,  529-531,  and  569-571.)  The  author  has  applied  the 
spectroscope  to  the  examination  of  tinctures  and  extracts  of  the 
following  drugs : — aconite,  belladonna,  bearberry,  buchu,  Indian 
hemp,  hemlock,  foxglove,  hops,  henbane,  lettuce,  lobelia,  matico, 
and  senna.  The  report  contains  many  points  of  interest,  but  as  it 
is  not  suited  for  abstraction,  we  must  refer  our  readers  to  the 
original  article. 

Valuation  of  Powdered  Ipecacuanha  Root  and  Dover's  Powder. 
T.  M.  Stewart.  {Amer.  Journ.  Pharm.,  August,  1876,  359.)  All 
the  specimens  were  obtained  from  different  retail  drug  stores  ia 
Detroit  and  Jackson,  Michigan. 

The  ipecacuanha  was  assayed  by  the  process  lately  recommended 
by  Dragendorff  ("  Werthbestimmung  einiger  starkwirkender  Dro- 
guen  "  (1874)  S.  37),  the  drug  being  extracted  first  by  acidulated 
water,  and  then  by  alcohol,  the  pectin  filtered  out  from  the  con- 
centrated solution ;  when  the  alkaloid  is  either  determined  volu- 
raetrically  by  potassium  mercuric  iodide,  or  extracted  by  chloro- 
form or  benzin  in  presence  of  barium  carbonate,  and  the  residue 
thereof  weighed  (one  c.c.  Mayer's  solution  precipitates  0'0189  gram 


264  TEAE-BOOK   OF    PHARMACY. 

emetia.)  Both  volumetric  and  gravimetric  ways  were  found  to  give 
concurring  duplicate  results,  and  the  two  wa^'s  gave  results  corre- 
sponding closely  "with  each  other ;  but  the  volumetric  method  leaves 
less  danger  of  loss  in  operating.     Two  grams  were  taken  each  time. 

Powdered  Ipecacuanha. 
No.  1.     1 'To  per  cent,  emetia.  No, 


1. 

1  'To  per  cent,  emetia. 

2_ 

l-i5 

3. 

2-10 

4. 

1-60 

5. 

1'90  per  cent,  emetia 

6. 

2-00 

7. 

1-90 

8. 

205 

Average,  1-84  per  cent,  emetia. 

All  the  numbers  were  examined  microscopically  and  chemically 
for  adulterations,  especially  for  almond  meal,  chalk,  and  antimonium 
potassium  tartrate  ;  but  no  adulterations  were  found,  except  a  little 
extraneous  woody  fibre. 

The  compound  powder  of  ipecacuanha  was  assayed  as  follows 
("Dragendorfi^'s  Werthbestimmung,"  S.  96).  Three  grams  of  the 
powder  were  extracted  with  85  per  cent,  alcohol  (the  residue  tests 
for  adulterations);  the  di*y  residue  from  the  alcohol  dissolved  in 
acidulated  (sulphuric  acid)  water,  filtering  if  necessary,  and  the 
narcotine  removed  by  washing  the  acid  solution  with  ether.  After 
addition  of  excess  of  barium  carbonate,  the  solution  is  now  extracted 
with  benzin  (several  portions),  the  residue  from  evaporation  of  the 
benzin  being  weighed  as  emetia  (confirming  by  dissolving  in  acid 
water  and  titrating  with  potassium  mercuric  iodide).  The  solution 
exhausted  with  benzin  is  washed  with  amylic  alcohol  (several  por- 
tions), and  the  residue  from  evaporation  of  the  amylic  alcohol 
weighed  as  morphia  (confirming  volumetrically  by  potassium 
mercuric  iodide  after  dissolving  in  acidulated  water).  The  ether 
and  the  amylic  alcohol  should  be  water  washed. 

Dover's  Foioder. 
0-20  per  cent,  emetia,  and  1-03  per  cent,  morphia. 
,,  1-00 
,,  1-06 
„  1-03 
„  0-93 
„  1-00 
„  106 
„  0-96 
.,  I'Ol 
,.,1-00 

The  average  of  O'lO  per  cent,  in  Dover's  Powder  equals  1'90  per 
cent,  emetia  in  ipecacuanha. 


No.  1. 

0-20 

„    2. 

0-16 

,,    3. 

0-23 

„    4. 

0-20 

„    5. 

013 

„    6. 

0-13 

„    7. 

0-26 

„    8. 

0-23 

Average 

,0-19 

S.  P.  Standard 

PHARMACY.  265 

All  the  samples  of  Dover's  Powder  were  examined  for  adultera- 
tions, organic  and  inorganic,  but  none  were  found. 

Benzol  and  Benzin.  M.  Heeren.  (Zeitsch-ift.  des  oesterr.  Apotli. 
Ver.,  1877,  190.)  The  terms  benzol  and  benzin  are  so  often  used 
indiscriminately,  not  merely  in  commercial  life,  but  also  in  chemical 
and  pharmaceutical  literature,  that  a  few  observations  respecting 
the  various  substances  which  pass  by  these  names  may  not  be  out 
of  place. 

Benzol,  when  first  discovered  by  Mitscherlich,  was  named  by  him 
benzin.  In  its  purest  condition,  as  obtained  by  distillation  from  a 
mixture  of  benzoic  acid  and  lime,  it  is  a  colourless  liquid  having  a 
pleasant  odour,  a  specific  gravity  of  '878,  and  a  boiling  point  of 
80'5°  C. ;  it  is  highly  infiammable,  can  be  ignited  at  ordinary  tem- 
perature, and  burns  with  a  luminous,  very  smoky  flame.  It  does 
not  mix  with  water,  but  combines  readily  and  in  all  proportions 
with  alcohol  and  fatty  oils.  It  takes  up  gutta  percha  in  vei'y  large 
proportion,  and  is  also  a  good  solvent  for  caoutchouc.  By  concen- 
trated nitric  acid  it  is  converted  into  nitrobenzol,  a  pale  yellow 
liquid  of  a  pleasant  odour,  resembling  that  of  the  essential  oil  of 
bitter  almonds.  When  cooled  to  0°  C,  it  solidifies,  forming  a 
crystalline  mass.  The  composition  of  benzol  is  represented  by  the 
formula  C^.  Hg,  and  its  high  percentage  of  carbon  (92"3)  fully  ac- 
counts for  the  dense  black  smoke  which  it  emits  on  burning. 

Much  cheaper,  bat  also  much  less  pure,  is  the  benzol  obtained 
from  coal  tar.  The  very  thin  liquid  known  as  coal  tar  oil,  which 
in  the  distillation  of  the  tar  passes  over  first,  yields  on  purification 
and  redistillation  a  product  consisting  principally  of  benzol,  but 
containing  also  toluol  (a  similar  but  less  volatile  liquid),  besides 
small  quantities  of  xylol,  cumol,  cymol,  and  probably  some  other 
less  volatile  hydrocarbons.  For  many  purposes  the  presence  of 
these  impurities  are  no  disadvantage  whatever,  and  in  benzol  re- 
quired in  the  manufacture  of  aniline  colours  the  presence  of  toluol 
is  even  an  essential  condition ;  but  it  is  only  just  to  insist  that  such 
a  preparation  should  be  distinguished  from  pure  benzol  by  its  name 
also,  as  will  be  the  case  if  this  product  be  always  called  benzin,  and 
the  name  benzol  be  restricted  to  the  preparation  obtained  from 
benzoate  of  lime. 

By  repeated  fractional  distillation,  it  is  possible  of  course  to  ob- 
tain from  coal  tar  oil  a  product  boiling  constantly  at  80°  C,  having 
a  specific  gravity  of  '88,  and  crystallizing  at  0°  C.  Such  a  prepa- 
ration is  now  an  article  of  commerce,  and  has  the  fullest  claim  to 
the  name  benzol ;  but  the  less  pure  products,  which  are  far  more 


266  YEAR-BOOK    OF    PHARMACY. 

common]}'  met  witli,  aud  are  sold  at  a  much  lower  price,  should  bo 
designated  as  benzin.  They  boil  at  a  higber  and  inconstant  tem- 
perature, and  the  determination  of  the  boiling  point  therefore  affords 
the  best  means  of  distinguishing  them  from  pure  benzol.  Their 
proper  name  is  benzin. 

Wholly  different  from  benzol  and  benzin,  and  yet  very  fre- 
quently confounded  with  them,  are  the  first  or  most  volatile  pro- 
ducts of  the  distillation  of  petroleum.  These  are  mixtures  of 
A-arious  hydrocarbons  of  different  boiling  points  and  specific  gravities, 
containing  among  others  the  hydrides  of  butyl,  amyl,  and  capryol. 
They  have  a  petroleum-like  odour,  quite  different  from  that  of 
benzol,  and,  when  shaken  with  an  equal  volume  of  alcohol  of  90 
per  cent.,  they  separate,  whereas  benzol  and  benzin  treated  in  the 
same  manner,  yield  perfectly  clear  and  uniform  mixtures.  Owing 
to  their  considerably  smaller  percentages  of  carbon,  they  burn  with 
a  much  less  smoky  flame  than  either  benzol  or  benzin.  To  prevent 
confusion,  these  products  ought  to  be  called  petroleum  benzin, 
petroleum  ether,  or  benzolin,  but  not  benzin. 

The  tars  obtained  fi'om  cannel  coal,  boghead  coal,  brown  coal, 
peat,  and  wood,  yield  mixtures  of  hydrocarbons  known  as  photogen, 
mineral  oil,  shale  oil,  and  eupione,  which  boil  at  a  much  higher 
temperature  than  benzol,  have  an  unpleasant  odour,  do  not  mix 
with  alcohol  of  DO  per  cent.,  and  burn  with  a  less  smoky  flame. 

The  Manufacture  of  a  Cinchona  Febrifuge  in  India.  (From  New 
Remedies,  v.,  386.)  The  cinchona  plantations  on  the  Neilghiris  yield 
practically  two  barks,  red  bark  and  crown.  Red  bark  is  rich  in 
total  alkaloids,  but  not  very  rich  in  quinia,  and  the  latter  is  diflBcult 
of  separation.  The  bark  is  of  comparatively  small  value,  therefore, 
to  the  quinine  maker,  although  of  great  value  to  the  government  as 
a  source  of  supply  for  a  cheap  febrifuge.  E.ed  bark  is  also  of  much 
value  in  Europe  for  making  galenical  preparations  (in  other  words, 
it  is  a  good  druggist's  bai'k),  and  recently  large  prices  have  been 
got  for  consignments  bought  by  druggists.  These  rates  are  far 
beyond  the  value  of  the  quinia  contained  in  such  bark,  as  estimated 
by  a  quinine-maker.  It  is  doubtful  whether  a  European  alkaloid- 
maker  could,  in  fact,  work  red  bark  for  its  alkaloids  at  their  present 
price,  and  pay  for  the  1)ark  at  the  rates  recently  given  in  London 
for  Neilghiri-grown  produce.  Crown  bark  is,  on  the  other  hand, 
rich  in  crystallizable  quinia,  and  is  nearly  as  highly  valued  by  the 
quinine-makers  as  good  American  yellow.  But  red-bark  trees  are 
by  far  the  most  numerous  on  the  government  and  other  plantations 
in  India  and   the  colonies.     This  species  is  hardier,  grows  better, 


PHARMACY.  267 

and  yields  about  one- third  more  bark  than  the  pale  or  crown  bark. 
The  utilization  of  red  bark  by  manufacture  in  India  is  therefore  of 
the  highest  importance. 

The  Sikkim  plantation  consists  of  red  and  yellow  bark  trees. 
Yellow  bark,  -which  has  been  a  failure  in  the  Neilghiris,  promises  to 
be  a  success  there.  In  character,  yellow  resembles  crown  bark,  but 
is  even  more  esteemed  by  the  quinine-makers.  As  both  are  easy  to 
work,  crown  and  yellow  barks  would  be  very  much  preferable  to 
red  bark  as  sources  for  the  manufacture  in  India  of  a  cheap  febri- 
fuge, if  officinalis  and  caUsaya  trees  could  be  got  to  grow  as  luxuri- 
antly as  sncciruhra. 

As  the  result  of  a  systematic  set  of  experiments,  Mr.  J.  Brough- 
ton,  government  quinologist  at  the  Neilghiri  plantation,  decided  on 
issuing  as  "  the  cheap  febrifuge  "  wanted  for  India,  a  preparation 
called  amorphous  quinine,  which  consisted  of  the  total  alkaloids  of 
cinchona  bark  in  the  form  of  a  non- crystalline  powder,  mixed  to 
some  extent  with  the  resin  and  red-colouring  matter  so  abundant  in 
red  bark.  This  alkaloid-mixture  was  accepted  by  the  medical  faculty 
in  the  Madras  Presidency  as  a  remedy  in  malarious  fever,  scarcely, 
if  at  all,  iuferor  to  quinia.  Of  these  alkaloids  about  six  hundred 
pounds  had  been  manufactured  up  to  the  end  of  the  fiscal  year 
1872-73,  when  it  was  found  that,  after  calculating  at  its  manu- 
facturing value  the  price  of  the  bark  used,  Mr.  Broughton's  product 
cost  more  than  ordinary  commercial  quinia.  The  factory  has  ac- 
cordingly been  closed,  and  the  bark  is  to  be  disposed  of  otherwise 
than  by  local  manufacture. 

The  Sikkim  (Himalaya)  plantations  ai^e  younger  than  those  on 
the  K"eilghiris.  No  quinologist  was  appointed  to  them  until  the 
end  of  the  year  IS 73,  when  Mr.  C.  H.  Wood  was  sent  out  by  the 
Secretary  of  State.     Actual  manufacture  did  not  begin  until  1875. 

The  method  at  present  in  operation  in  the  factory  in  Sikkim  is 
simple  in  the  extreme,  and  is  as  follows  : — 

General  Nahire  of  the  Process. — The  dry  bark  is  crushed  into  small 
pieces  (but  not  powdered),  and  is  put  into  wooden  casks,  where  it 
is  macerated  in  the  cold  with  very  dilute  hydrochloric  acid.  The 
liquor  is  then  run  off  into  wooden  vessels,  and  mixed  with  an  excess 
of  a  strong  solution  of  caustic  soda  ;  a  precipitate  forms,  which  is 
collected  on  calico  filters,  and  well  washed  with  water.  The  preci- 
pitate is  then  dried  at  a  gentle  heat  and  powdered.  It  constitutes 
the  crude  fehrifuge,  which  is  next  submitted  to  a  process  of  purifica- 
tion. In  the  latter  process  a  certain  weight  of  the  crude  product  is 
dissolved  in  dilute  sulphuric  acid,  and  a  small  quantity  of  a  solution 


2C8  TEAR-BOOK    OF   PHARMACY. 

of  sulphur  in  caustic  soda  is  added  to  the  liquor.  After  the  elapse  of 
twenty-four  hours,  the  liquor  is  carefully  filtered,  the  filtrate  is 
mixed  with  the  caustic  soda,  and  the  resulting  precipitate  collected 
on  calico,  washed  with  a  small  quantity  of  Avater,  dried  and  pow- 
dered ;  it  is  then  ready  for  issue,  and  is  sent  out  under  the  name  of 
'■  Cinchona  Febrifuije." 

Arraufjement  of  the  Factory  Sheds. — A  position  was  chosen  con- 
veniently near  the  dry  bark  godowns,  and  so  situated  on  the  side 
of  the  hill  that  a  copious  supply  of  water  could  be  obtained  at 
a  level  with  the  roof  of  the  sheds  in  which  the  maceration  is  con- 
ducted. 

These  sheds  are  rough  temporary  erections,  constructed  with  sap- 
lings, and  a  mat  or  thatch  roof.  Down  the  centre  an  open  drain  is 
cut  to  carry  ofi"  the  waste  liquor.  Over  this  drain  some  wooden 
stands  are  placed,  on  which  the  calico  filters  rest.  The  filters  are 
formed  by  tying  a  square  piece  of  calico  to  a  wooden  frame  by  the 
four  corners.  On  each  side  of  the  shed  is  placed  a  row  of  twenty- 
one  casks,  standing  on  end  upon  a  stand  which  elsvates  them  about 
two  feet  from  the  ground.  They  are  empty  beer-barrels,  which 
have  been  purchased  from  the  Commissariat  Department  at  Darjeel- 
ing,  the  head  removed,  and  the  cask  thoroughly  cleansed  ;  a  hole  is 
cut  in  the  side  of  the  cask  at  a  level  with  the  bottom,  and  closed 
with  a  cork.  In  front  of  the  casks  a  row  of  tubs,  formed  by  cutting 
beer-barrels  in  halves,  is  placed,  so  that  on  uncorking  the  barrels, 
the  liquor  will  ran  oat  into  the  tubs. 

Outside  the  shed,  at  one  end,  are  a  couple  of  large  wooden  vats 
at  such  an  elevation  that  liquid  can  flow  from  them  along  a  bamboo 
trough  into  any  one  of  the  barrels  in  the  shed.  The  cajmcity  of  the 
large  vats,  up  to  a  mark  on  the  inside  near  the  top,  is  accurately 
determined.  Water  is  run  into  the  vat  up  to  the  mark,  and  a  cer- 
tain quantity  of  muriatic  acid  is  added,  and  the  whole  well  mixed. 
This  diluted  acid  can  then  be  run  into  any  one  of  the  casks  in  a  line 
with  the  vat,  by  means  of  a  bamboo  trough.  In  addition  to  the 
macerating  sheds,  thei'e  is  a  small  brick  building,  heated  with  char- 
coal, in  which  the  precipitate  is  dried;  also  a  sej)arate  shed  in  which 
the  process  of  purification  is  conducted. 

Method  of  Conducting  the  Process. — The  casks  are  worked  in  sets 
of  three,  and  are  marked  ABC. 

In  each  shed  there  are  fourteen  sets,  seven  on  each  side.  Each 
cask  receives  one  maund  (  =  37|  kilos.)  of  dry  bark,  which  undergoes 
four  successive  macerations,  the  liquor  being  moved  in  rotation 
through  the  three  casks.     Each  maceration  lasts  half  a  week.     The 


PHARMACY.  269 

liquid  used  for  the  fourtli  and  last  maceration  is  acidulated  water 
drawn  from  the  vat.  "When  this  is  run  off,  it  is  moved  into  the  next 
cask  to  form  the  third  h'quor.  When  this  is  drawn  off,  it  forms 
the  second  h'quor  for  another  cask,  and,  when  transferred  from  that, 
it  goes  on  to  new  bark,  from  which  it  is  drawn  off  and  precipitated. 
Of  course,  in  starting  a  new  shed,  every  cask  contains  dry  bark, 
consequently  the  system  of  rotation  is  not  brought  into  fall  operation 
until  after  the  first  fortnight ;  and  it  is  only  after  the  shed  has  been 
in  operation  for  three  and  a  half  weeks  that  the  liquor  for  precipi- 
tation has  been  used  for  four  macerations. 

The  liquor  which  is  to  be  precipitated  is  now  run  into  the  tubs. 
The  other  hquors  are  drawn  into  wooden  buckets  and  poured  into  the 
proper  casks.  The  new  acid  is  then  drawn  from  the  vats.  The 
diluted  acid  is  made  in  the  vat  by  adding  one  gallon  of  muriatic 
acid  to  every  one  hundred  gallons  of  water. 

The  weight  of  acid  used  in  the  exhaustion  is  6|  per  cent,  of  the 
weight  of  dry  bark.  It  is  obtained  from  Mr.  Waldie's  chemical 
works,  at  a  cost  of  3|^  annas  (8  annas  =  1  shilling  Engl.)  per  pound 
in  Calcutta. 

To  precipitate  the  saturated  liquor,  a  solution  of  caustic  soda  is 
added  in  excess.  The  caustic  soda  is  obtained  from  England  in 
o-cwt.  drums,  costing  from  £15  to  £20  per  ton  in  London.  One 
part  of  this  is  dissolved  in  three  parts  of  water,  and  the  solution 
stored  in  iron  vessels.  The  quantity  to  be  added  to  the  bark  liquor 
must  be  judged  of  by  the  appearance  produced.  When  a  sufficient 
quantity  has  been  introduced,  the  precipitate  assumes  a  somewhat 
curdy  condition. 

About  G^  pounds  of  solid  soda  are  used  for  every  100  pounds  of 
dry  bark. 

The  filtration  is  not  commenced  until  the  following  day,  when 
the  liquor  is  transferred  to  the  calico  strainers,  which  have  been 
well  wetted.  The  first  portions  that  run  through  are  returned,  until 
the  liquid  passes  of  a  bright  ruby  colour ;  it  is  then  allowed  to  flow 
away  by  the  drain.  After  all  the  liquor  has  drained  off,  water  is 
passed  through  the  precipitate  until  it  ceases  to  acquire  a  red  tint. 
The  alkaloids  on  the  filter  should  then  be  of  a  uniform  cream  colour. 
The  precipitate  is  now  dried  and  reduced  to  a  fine  powder,  which 
is  stored  in  suitable  bins.     It  constitutes  the  crude  febrifuge. 

The  Process  of  Purification. — The  precipitate  during  the  act  of 
drying  acquires  a  slightly  reddish  brown  colour.  It  is  therefore 
submitted  to  a  process  of  purification.  Fourteen  gallons  of  water 
are  mixed  with  two  pints  of  sulj^huric  acid,  and  twenty  pounds  of 


270  YEAR-BOOK    OF    PHARMACY. 

the  dry  powder  are  introduced.  The  alkaloids  dissolve,  and  a  quan- 
tity of  colouring  matter  remains  insoluble.  About  half  a  pint  of  a 
solution  of  sulphur  in  caustic  soda  is  now  stirred  in,  and  the  -whole 
allowed  to  stand  for  twenty-four  hours.  It  is  then  filtered  through 
calico  into  a  clean  vessel,  care  being  taken  to  get  the  liquor  perfectly 
bright.  About  six  gallons  of  water  are  used  to  wash  the  sediment 
left  on  the  filters.  The  clear  filtrate  is  thoroughly  mixed  with  solu- 
tion of  soda  to  precipitate  the  alkaloids  ;  the  precipitate  is  collected 
on  calico,  washed  with  a  small  quantity  of  water,  drained,  dried, 
and  reduced  to  fine  powder  ;  it  is  then  ready  for  issue. 

Wooden  tubs  are  used  for  this  process,  but  they  are  not  so  well 
suited  for  the  purpose  as  enamelled  iron  or  earthenware.  The 
purification  is  conducted  iu  a  separate  shed  by  a  man  who  is  con- 
fined to  that  work. 

The  Labour  employed. — The  only  workmen  employed  in  the  factory 
are  Nepaulese  coolies.  When  the  process  is  once  brought  into  full 
operation  it  is  found  that  these  men  readily  master  every  detail,  and 
conduct  the  whole  thing  with  all  the  care  and  accuracy  that  is 
required.  But,  of  course,  the  factory  is  under  the  supervision  of 
Mr.  Grammie,  the  officer  in  charge]  of  the  plantation,  who  visits  it 
once  a  day,  and  sees  that  the  work  is  being  properly  performed. 

The  Baric  used. — Di*y  succiruhra  bark  only  is  employed.  More- 
over, care  is  taken  to  mix  the  root,  stem,  and  branch  bark  together 
in  as  nearly  as  possible  the  proportions  in  which  they  are  yielded 
by  the  plantations.  This  mixture  is  broken  into  small  pieces,  and  a 
maund  of  it  goes  into  each  cask.  This  is  done  to  insure  uniformity 
of  composition  in  the  product.  Green  bark  is  never  operated  on. 
It  will  be  seen  that  the  arrangement  of  the  process  requires  that  a 
certain  weight  of  bark  should  be  put  into  the  casks  every  week 
throughout  the  year.  This  could  not  be  done  with  green  bark, 
l^ecause  bark  is  only  taken  from  the  trees  twice  per  annum.  Apart 
from  this,  however,  it  has  been  found  that  dry  bark  yields  a  much 
better  product,  and  quite  as  large  a  quantity.  The  small  cost  of 
drying  the  bark  is  more  than  counterbalanced  by  the  advantages 
gained. 

Temporary  Ohject  of  the  Process. — It  must  be  remembered  that 
this  method  has  only  been  adopted  to  furnish  a  large  supply  of 
febrifuge  for  trial ;  it  does  not  profess  to  make  the  most  economical 
use  possible  of  the  bark.  The  factory  is  estimated  to  turn  out 
during  the  present  financial  year  4800  pounds  of  febrifuge,  which, 
at  a  rupee  an  ounce,  will  pay  the  whole  cost  of  the  plantations  and 
manufacture  for  the  year.     If  the  product  proves  to  be  of  permanent 


PHARMACY.  271 

value  as  a  remedial  agent,  it  is  probable  tliat  the  process  will  be 
considerably  modified  to  produce  greater  economy,  but  involving 
the  use  of  permanent  buildings  and  machinery. 

Toxicological  Studies  upon  Copper  and  its  Compounds.  L.  M.  V. 
Galippe.  (Journ.  de  Fharvi.  et  de  Chim.,  xxiii.,  298.)  The  results 
of  numerous  experiments  with  dogs  led  the  author  to  the  conclusion 
that  copper  salts  do  not  produce  fatal  effects.  A  dog  weighing  8 
kilograms  received  daily  doses  of  '5  gram  of  neutral  acetate  of 
copper  for  124  days.  During  that  time  it  was  troubled  with 
diarrhoea  and  vomiting,  but  it  never  lost  its  appetite. 

It  was  then  killed,  and  its  liver  (weighing  2G0  grams)  found  to 
contain  "SI  gram  of  copper  =  1"121  sulphate.  The  animal  had  in  all 
consumed  72  grams  of  the  acetate.  43  grams  of  sulphate  of  copper 
were  administered  to  a  dog  in  the  course  of  122  days  ;  65  grams  to 
another  within  151  days;  47  grams  to  a  third  within  107  days  ;  and 
98  grams  to  the  fourth,  a  bitch,  during  150  days.  The  liver  of  the 
last  one  weighed  310  grams,  and  contained  '223  gram  of  copper  = 
"87  gram  of  the  sulphate.  During  the  experiments  this  last  dog  had 
pupped,  and  the  livers  of  the  young  were  likewise  found  to  contain 
copper.  Traces  of  this  metal  were  also  detected  in  the  milk.  Other 
copper  compounds,  viz.  the  ammonio-sulphate,  lactate,  citrate,  tar- 
trate, malate,  oxalate,  oxide,  subchloride,  and  subacetate  (verdigris), 
yielded  similar  results. 

The  workmen  engaged  in  the  verdigris  factories  at  Montpellier 
are  reported  not  to  suffer  in  health  from  their  occupation.  The 
urine  of  these  workmen  always  contains  copper. 

Purification  and  Pharmaceutical  Application  of  Petroleum.  M. 
Masson.  {Eepert.  dePharm.,lS76,  742.)  The  author  frees  petro- 
leum from  its  unpleasant  odour  in  the  following  manner: — 

60  grams  of  strong  sulphuric  acid  and  the  same  quantity  of 
strong  nitric  acid  are  slowly  poured  into  100  kilograms  of  petroleum 
by  means  of  a  funnel  having  a  long  tube ;  after  this,  500  grams  of 
strong  alcohol  are  carefully  poured  on  the  surface  of  the  oil.  The 
alcohol  sinks  down  gradually,  and  on  reaching  the  layer  of  acids 
causes  a  slight  effervescence  and  evolution  of  heat.  Ethereal  pro- 
ducts of  a  pleasant  odour  are  thus  evolved  and  communicated  to 
the  oil,  which  at  the  same  time  assumes  a  yellowish  colour.  The 
reaction  lasts  about  an  hour  ;  the  oil  is  then  gently  agitated  with 
water,  and  the  mixture  allowed  to  settle. 

Petroleum  thus  purified  might  take  the  place  of  alcohol  in  lini- 
ments, tincture  of  arnica,  and  other  tinctures  and  preparations  in- 
tended for  external  application. 


272  YEAR-BOOK   OP    PHARMACY. 

Tlie  bottom  layer  (a  mixture  of  acids,  water,  and  alcohol)  may  be 
used  for  deodorizing  the  heavy  oils  of  petroleum,  by  agitating  them 
with  this  mixture,  then  allowing  to  settle  for  twelve  hours,  de- 
canting, and  washing  with  lime  milk  to  completely  remove  the  acid. 

Chlorine  as  an  Antidote  to  Prussia  Acid.  M.  Gautier.  {Bull. 
Soc.  Chim.,  1876,  433.)  Experiments  made  upon  rabbits,  in  order 
to  test  the  value  of  inhalations  of  chlorine  as  an  antidote  to  prussic 
acid,  proved  very  successful.  Fatal  doses  of  the  poison  were  ad- 
ministered, and  the  gas  applied  a  few  minutes  after  death  had 
apparently  set  in,  whereby  in  the  majority  of  cases  the  animals 
recovered.     The  same  effect  was  observed  ^-ith  insects. 

The  Comparative  Merits  of  Phosphide  of  Zinc  and  Phosphorus  as 
Therapeutic  Agents.  {New  Remedies,  1877,  48.)  The  phosphide 
of  zinc  has  so  far  proven  a  most  efficient  agent  in  the  successful 
treatment  of  the  major  part  of  a  certain  class  of  aflfections.  In  very 
many  instances  it  has  been  far  more  curative  than  phosphorus. 
Considered  in  the  light  of  a  curative  agent,  the  phosphide  of  zinc 
stands  alone,  not  only  for  the  certainty  but  for  the  rapidity  of  its 
action  as  a  nervous  tonic  and  stimulant.  Its  value  in  these  respects 
has  of  late  been  fairly  tested  in  the  last  and  exhausting  stages  of 
typhoid  and  other  fevers,  where  the  nervous  energies  have  been  so 
far  prostrated  as  to  render  convalescence,  if  not  doubtful,  at  least 
tedious  and  protracted.  The  great  therapeutic  value  of  the  phos- 
phide of  zinc  is  evinced  in  the  most  distinct  manner,  when  used  in 
the  treatment  of  neuralgia.  "While  the  phosphorus  is  seldom 
curative  in  doses  less  than  one-twentieth  of  a  grain,  often  calling 
for  as  much  as  one-tenth  or  one-fourth,  the  phosphide  of  zinc  yields 
as  reliable  and  more  speedy  i-esults  in  doses  of  one-tenth  to  one- 
cio-hth  of  a  grain.  But  few  stomachs  can  tolerate  more  than  one- 
thirtieth  of  a  gi'ain  of  phosphorus  before  manifesting  symptoms  of 
irritation,  which,  in  connection  with  the  "matchy  "  taste  soon  evolved 
in  eructations,  often  engenders  a  disgust  to  its  further  continuance. 
Nor  are  these  disagreeable  features  altogether  abolished  by  any  of 
the  multitudinous  formulse  now  in  vogue.  On  the  other  hand,  ex- 
perience with  the  phosphide  of  zinc  has  proven  that  it  enters  the 
circulation  far  more  rapidly  than  the  element,  and  when  administered 
in  doses  of  from  one-eighth  to  one-twelfth  of  a  grain,  it  produces 
its  curative  influence  far  more  readily,  and  is  equally  as  permanent 
in  therapeutic  power.  It  has  been  found  to  be  extremely  serviceable 
in  neuralgia  in  doseS  of  one-eighth  of  a  grain  in  the  form  of  a  pill, 
in  angina,  in  loss  of  memory,  and  impotence,  in  loss  of  sleep  from 
continued  mental  anxiety,  and  generally  in  those  nervous  affections 


PHARMACY. 


273 


that  owe  their  origin  to  exhaustiou  and  depression  of  the  nerve  force. 
J)r.  Hammond's  formula  is  one-sixteenth  of  a  grain  of  phosphide  of 
zinc,  with  one-fourth  of  a  grain  of  extract  of  nux  vomica,  made  into 
a  pill. 

The  Use  of  Glycerin  in  Fluid  Extracts.  J.  W.  Lehman.  (From 
an  inaugural  essay.  Amer.  Journ.  Pharm.,  1877,  34G.)  A  number 
of  experiments  were  made  with  officinal  and  unofficiual  fluid  ex- 
tracts, with  the  view  of  determining  the  preservative  qualities  of 
glycerin  in  this  class  of  preparations.  The  results  obtained  may  be 
tabulated  as  follows  :  — 


Fluid  Extract  of 

Menstruum. 

Remarks. 

Aconite  root     .     . 

Alcohol  3  p.,  glycerin 

Dark  reddish   brown,    after    two 

Ip. 

weeks  muddy ;  filtered,  became 
again  turbid. 

,,         ,,        .     . 

Alcohol     .... 

Of  lighter  colour  ;  remained  clear. 

Asclepias  tuberosa 

Dil.  alcohol  3  p.,  gly- 
cerin 1  p. 

Gelatinized  in  four  weeks. 

,,            ,, 

Alcobol  2  p.,  water  & 

Did  not  gelatinize ;  sHght  precipi- 

glycerin each  1  p. 

tate. 

Buchu     .... 

Alcohol  3  p.,  glycerin 

Ip. 
Officinal    .... 

Dense  precipitate  in  five  days. 

Conium  (leaves  ?) . 

Dark  and  clear ;  slight  precipitate 

in  two  weeks. 

Digitalis  .... 

,,          .... 

!I                                          I)                                      11 

Ergot 

,,          .... 

,,                                          ,,                                        ,, 

Grindelia  robusta . 

Dil.  alcohol  3  p.,  gly- 
cerin 1  p. 

,> 

Hyoscyamus     .     , 

Officinal    .... 

71                                         )(                                      )1 

Krameria      .     .     . 

Brown-red;  clear. 

Pruuus  Yirginiaua 

.... 

Soon  turbid,  and  considerable 
precipitate. 

»               .) 

"Water  8  fl.oz.,  after- 

Shght precipitate  after  four  weeks. 

wards  glycerin  and 

dilute  alcohol  equal 

parts 

Stramonium     .     . 

Officinal    .... 

Dark  and  clear  ;  shght  precipitate 
on  standing. 

Valeriana     .     .     . 

Eemaius  clear. 

,,            ... 

Alcohol  3  p.,  glycerin 

Very  muddy  in  two  weeks  ;    fil- 

Ip. 

tered,  muddy  again  in  one  week. 

„            ... 

Alcohol  3  p.,  glycerin 

Slight  precipitate  in  two  weeks  ; 

Ip. 

filtered,  very  slight  change 
afterwards. 

Zingiber .... 

Officinal    .... 

Eemains  clear. 

,1       .... 

Alcohol,   with   small 

Precipitated  some  in  five  days. 

prop,  of  glycerin. 

The  author  concludes  that  the  use  of  glycerin  in  fluid  extracts  of 
astringent  drugs  adds  much  to  the  beauty  and  stability  of  the 
preparation.     Its  use  appears   also  to  be  indicated  for  drugs  the 

T 


274  YEAR-BOOK    OF    PHARMACY. 

active  principles  of  -wliicli  are  soluble  in  water  and  dilute  alcohol. 
In  fluid  extracts  of  mucilaginous  drugs  like  pleurisy  root  it  cannot 
be  used  to  any  great  extent,  and  it  is  best  discarded  altogether  in  all 
cases  where  the  active  principle  is  of  a  resinous  nature. 

Salicylic  Acid  in  Diphtheritis.  Dr.  Wagner.  (Zeifschr.  cles 
oesterr.  Ajpoth.  Ver.,  1876, 441.)  The  author  reports  most  favourably 
on  the  curative  effects  of  salicylic  acid  in  diphteritis.  To  children 
too  young  to  use  a  gargle  he  administered  "15  to  '3  gram  of  the 
powdered  acid  in  water  or  wine  every  two  hours  ;  older  ones  were 
treated  at  the  same  time  with  a  gargle  containing  1'5  gram  of  the 
acid  and  15  grams  of  rectified  spirit  to  150  grams  of  water,  this 
gargle  being  applied  every  hour.  Of  fifteen  severe  cases  treated  in 
this  manner,  not  one  terminated  fatally.  Recovery  took  place  far 
more  rapidly  than  the  author  had  ever  witnessed  in  cases  treated 
with  other  remedies. 

Sulphurous  Acid  as  an  Antiseptic  and  Antifermentative  com- 
pared with  Salicylic  Acid.  M.  Baierlacher.  (Phannaceid.  Cen- 
tralhalle,  1877,  148.)  The  author  has  arrived  at  the  following 
conclusions  : — 

1.  Sulphurous  acid  is  more  powerful  than  salicylic  acid  in  its 
antifermentative  action  on  yeast. 

2.  Sulphui'ous  acid  prevents  the  formation  or  growth  of  mould  ; 
in  this  respect  carbolic  acid  stands  nearer  to  it  than  salicylic. 

3.  The  action  of  emulsin  and  of  myrosin  is  retarded  by  sulphurous 
acid  moi'e  than  by  salicylic  acid  ;  but  it  is  not  entirely  prevented 
unless  the  acid  be  used  in  large  quantity. 

4.  Putrefaction  is  effectually  retarded  by  sulphurous  acid.  The 
author  strongly  recommends  the  application  of  burning  sulphur  for 
the  disinfection  of  rooms,  and  the  local  application  of  sulphurous 
acid  in  diphtheritis. 

The  Strength  of  Tinctura  Opii.  J.  M.  Maisch.  (Amer.  Journ. 
Pharm.,  1877,  511.)  The  strength  of  tincture  of  opium  as  ordin- 
arily sold  has  been  the  subject  of  investigation  by  three  students  of 
the  Philadelphia  College  of  Pharmacy,  class  1876-77.  Mr.  Jos. 
Stable  Smith  merely  determined  the  amount  of  extract  left  on  the 
evaporation  of  one  fluid  ounce  of  the  tincture,  five  samples  giving 
the  following  results :  21-5,  15,  11-5,  9*5,  and  8  grains.  Each  fluid 
ounce  represents  3 7' 5  grains  of  dry  opium,  which  on  an  average 
yields  60  per  cent.,  or  22*5  grains  of  extract ;  the  presumption, 
therefore,  is  that  of  the  five  samples  examined  only  one  was  made 
in  accordance  with  the  U.S.  Pharmacopoeia, 

Mr.  Wm.  H.  Llewellyn  ascertained  not  only  the  amount  of  ex- 


PHARMACY.  ?.70 

tract,  but  separated  also  the  morphia  from  one  fluid  ounce  of  com- 
mercial laudanum,  using  for  the  latter  operation  a  modification  of 
Staples'  process ;  his  results  were  as  follows  : — 

Extractfroml  fluid  ounce,  15-  15-  16-  15-o0  23-25  28-75  30-  32-  37'  39-50  gr. 
Morphia     „  „  4-     3-75     3-     3-25     2-         1-75     1-     1-       -5  trace. 

Opium  of  officinal  strength  should  yield  3' 75  grains  of  morphia 
per  fluid  ounce  of  latidanum.  While  some  of  the  samples  come  up 
to  this  requirement,  it  is  noteworthy  that  they  fall  short  in  the 
amount  of  extractive  matter  as  usually  met  with  in  Smyrna  opium  ; 
on  the  other  hand,  it  is  plain  that  at  least  one-half  of  these  tinc- 
tures, which  are  very  deficient  in  morphia,  were  artificially  coloured, 
with  the  view  of  imparting  an  appearance  of  strength  which  they 
did  not  possess. 

Another  series  of  experiments  with,  laudanum  sold  at  retail  was 
made  by  Mr.  Burt  P.  Gates,  who  determined  the  specific  gravity  at 
60°  F.  by  means  of  a  1000-grain  bottle,  and  made  two  morphio- 
metric  assays,  following  Staples'  process  with  some  modifications  ; 
his  results  are  tabulated  as  follows  : — 

Specific  Gravity. 
•965     -952  -962  -956  -958  -955  -953  -949  -956  -943  -947  -956  -939  -950  -881 

Morphia  per  fluid  ounce. 
3-85    3-70  3-54  3-39  2-96  2-62  2-77  2-46  2-16  208  2-00  1-85  103  1-39  0-77 

Percentage. 
10-3      9-9     9-4    9-0     7-8     7-0     7-4    6-6     5-7     56    5-3     4-9     4-4    37     2-1 

Only  three  of  these  samples  can  be  assumed  to  have  been  made 
from  well-dried  opium ;  five  appear  to  have  been  made  from  imper- 
fectly dried  or  from  more  or  less  moist  opium  ;  the  remaining 
seven,  of  which  five  are  also  deficient  in  density,  have  apparently 
been  made  of  less  opium  than  officially  directed. 

A  New  Method  for  the  Preparation  of  Extracts  without  Heat. 
A.  Herrara.  (Chem.  and  Drugg.,  1877,  390.)  The  fact  that 
when  water  is  partially  frozen  the  dissolved  matters  remain  in  the 
mother  liquor  has  been  used  commercially  in  a  variety  of  ways  for 
some  years  past.  Impressed  with  the  fact  that  even  a  moderate 
degree  of  heat  seriously  modifies  the  properties  of  most  vegetable 
substances,  the  author  proposes  that  the  process  just  mentioned 
should  be  adopted  for  the  preparation  of  extracts.  The  actual  pro- 
cess is  as  follows  : — The  freshly  expressed  juice,  or  the  cold  water 
infusion,  is  placed  in  some  such  apparatus  as  that  used  for  making 
ice  cream,  and  surrounded  with  a  mixture  of  crystallized  chloride 


276  YEAR-BOOK    OF    PHAKMACY. 

df  >calcium  or  chloride  of  sodium  and  pounded  ice.  The  juice  is 
allowed  to  remain  till  a  large  portion  has  congealed,  the  mass  of  ice 
is  enclosed  in  a  cloth  and  subjected  to  pressui'e,  the  press-cake  is 
broken  and  again  pressed,  to  separate  the  mother  liquor  as  com- 
pletely as  possible.  The  expressed  mother  liquor  is  mixed  with  the 
bulk,  and  the  congelation  is  repeated  two  or  three  times,  with  the 
precaution  that  it  must  not  be  carried  far  enough  to  precipitate  any 
of  the  more  sparingly  soluble  principles.  The  mother  liquor  is  then 
put  into  shallow  dishes  and  exposed  to  the  heat  of  the  sun  or  of  a 
drying  room,  the  temperature  of  which  does  not  exceed  30°  C.  (86° 
Fahr.),  until  the  extract  has  attained  the  desired  consistence. 

Extract  of  conium,  prepared  with  unpurified  juice  by  the  process 
mentioned,  has  preserved  the  characteristic  odour  of  conia,  and  by 
dissolving  it  in  water  the  author  obtained  a  solution  exactly  repre- 
senting the  juice  of  the  plant  in  appearance  and  properties,  and 
giving,  when  heated,  an  abundant  coagulation,  proving  that  even 
albumen  had  remained  unaltered.  1,750  grams  of  cow's  milk,  of 
9°  B.,  left,  after  three  congelations,  750  grams  of  a  liquid  having  a 
density  of  14°,  and  by  evaporation  in  the  sun  this  left  a  dry  extract 
of  milk,  which  again  formed  that  liquid  on  being  dissolved  in  water. 
Extract  of  rhatauy,  prepared  by  the  process  of  congelation,  dissolves 
completely  in  water,  with  a  red  colour,  and  has  a  much  more  as- 
tringent taste,  compared  with  an  extract  which  was  prepared  with 
the  utmost  precaution  by  evaporation  in  a  water  bath.  Similar 
comparisons  were  made  with  the  extracts  of  catechu,  aloes,  and 
others,  and  in  all  cases  a  very  notable  diflference  was  observed, 
which  is  explained  by  the  final  evaporation  in  the  proposed  process 
being  conducted  by  the  heat  of  the  sun  or  of  the  drying  closet, 
which  is  insufficient  to  efi"ect  a  change  or  to  volatilise  the  volatile 
principles  in  any  appreciable  degree. 

It  may  be  objected  that  the  vegetable  juices  should  be  previously 
purified ;  but  it  should  be  remembered  that  coagulated  albumen 
always  encloses  a  considerable  portion  of  the  active  principles,  and 
that  the  heat  necessary  to  effect  the  coagulation  and  the  evaporation 
by  means  of  a  water  bath  is  sufficient  to  change  mauy  principles ; 
also,  that  the  extracts  thus  prepared  are  sometimes  inert  or  less 
active.  The  careful  experiments  made  by  Orfila  and  the  clinical 
experience  of  others  demonstrate  that  extracts  prepared  with  un- 
purified juice  are  the  stronger. 

For  the  extracts  prepared  from  juices  by  the  method  indicated, 
the  author  proposes  the  designation  of  opopycnols,  derived  from  the 
two  Greek  words  meaning ^iu'cc  and  to  condense. 


PHAKMACT.  277 

Iodide  of  Starch  as  an  Antidote  to  Poisons.  Dr.  Bellini. 
(Rcpert.  de  PJiarm.,  1877,  17;  Jouni.  do  Med.  de  Braxelles,  1877, 
174)  In  a  paper  read  before  the  Medical  Society  of  Florence,  the 
author  recommends  iodide  of  starch  as  a  valuable  antidote  in  cases 
of  poisoning  by  caustic  alkalies,  alkaline,  or  earthy  sulphides,  and 
vegetable  alkaloids.  The  preparation  is  easily  administered  in  large 
doses,  does  not  possess  the  irritating  properties  of  free  iodine,  and 
readily  forms  harmless  compounds  with  the  substances  named.  To 
avoid  the  subsequent  decomposition  of  the  latter,  its  administration 
may  be  followed  by  an  emetic.  As  an  antidote  to  alkaline  and 
earthy  sulphides,  the  author  thinks  it  preferable  to  all  others.  In 
cases  of  poisoning  by  ammonia,  caustic  potash,  or  soda,  it  is  applic- 
able when  acid  drinks  are  not  at  hand. 

The  Decolorization  of  Iodide  of  Starch.  A.  Vogl.  (Neues 
Bepert.  f.  Phann.,  1876,  565.)  The  disappearance  of  the  blue 
colour  of  iodide  of  starch  at  a  temperature  of  70°  to  90°  C,  is  par- 
tially due  to  the  volatilization  of  iodine.  A  piece  of  starch  paper 
held  over  the  flask  in  which  the  liquid  is  heated,  turns  blue.  On 
boiling  the  liquid  for  some  time,  the  evolution  of  iodine  vapour 
ceases,  and  when  this  point  is  reached,  the  blue  colour  is  no  longer 
restored  on  cooling. 

The  statement  occurring  in  many  books  that  iodine  may  thus  be 
completely  expelled  from  its  combination  with  starch,  is  not  con- 
firmed by  the  author's  experiments.  Even  after  prolonged  boiling, 
and  long  after  the  solution  has  ceased  to  resume  its  blue  coloiu' 
upon  cooling,  it  is  immediately  turned  blue  on  the  addition  of 
nitric  acid,  chlorine,  etc.  In  the  same  manner  the  px'esence  of 
iodine  can  be  shown  in  the  horny  translucent  residue  left  on  evapo- 
ration of  the  solution.  The  author  thinks  that  the  iodine  exists  in 
this  residue  in  the  form  of  a  very  stable  and  probably  definite  com- 
bination calling  for  further  investigation. 

Under  the  influence  of  sunlight  a  solution  of  iodide  of  starch  also 
loses  its  colour,  which  is  restored  by  nitric  acid. 

The  Preservation  of  Pulvis  Ergotse.  (Ghem.  and  Bnigg.,  from 
Journ.  Therapeutique.)  Divers  plans  have  been  proposed  for  the  pre- 
servation of  powdered  ergot,  which  should  retain  its  physiological 
properties  unimpaired.  Appert  proposed  the  employment  of  balsam 
of  tolu.  M.  Bories  recommends  that  a  little  mercury  should  be 
kept  at  the  bottom  of  the  vessel  containing  it.  Othei's  have  recom- 
mended that  alcohol  should  be  used  in  the  same  way.  All  these 
processes  necessitate  that  the  powder  should  be  prepared  when 
required,  as  it  is  much  more  alterable  than  the  fungus  itself. 


278  YEAR-BOOK    OF    PHARMACY. 

Towards  the  end  of  1874  the  authora  powdered  100  grams  of  care- 
fully selected  ergot.  50  grams  were  placed  in  a  dry  bottle ;  the 
other  50  grams  were  mixed  with  5  per  cent,  of  powdered  benzoin, 
and  set  aside  in  a  similar  bottle.  Both  bottles  were  placed  in  the 
laboratory,  with  their  mouths  simply  covered  with  a  card.  Four- 
teen months  afterwards  the  benzoinated  powder  was  unchanged, 
while  the  other  was  an  odoriferous  mass  of  living  matter.  The 
powder  thus  preserved  was  found  thoroughly  reliable  by  several 
eminent  obstetricians. 

The  Purity  of  Chloral  Hydrate.  C.  Annessens.  {Journal  de 
Pharm.  d'Ancers,  1877,  1.)  The  formation  of  white  fames  on  ap- 
proaching chloral  hydrate  with  a  glass  rod  moistened  with  solution 
of  ammonia  has  been  frequently  regarded  as  an  indication  of  the 
presence  of  hydrochloric  acid,  and  consequently  as  a  proof  of  the 
unfitness  of  the  preparation  for  medicinal  use.  The  author  shows 
these  conclusions  to  be  erroneous.  Perfectly  pure  chloral  hydrate  at 
any  but  very  low  temperatures  always  fumes  when  brought  near 
ammonia,  and  the  presence  of  hydrochloric  acid  can  only  be  demon- 
strated by  means  of  silver  nitrate.  The  white  cloud  which  is  formed 
from  the  fumes  of  ammonia,  and  the  volatilized  vapour  of  chloral 
hydrate,  is  due  to  the  formation  of  ammonium  formiate.  This  may 
easily  be  proved  by  absorbing  the  vapour  of  chloral  with  a  piece  of 
blotting-paper  saturated  with  ammonia;  an  abundant  white  cloud  is 
produced.  The  paper  is  washed  with  distilled  water,  the  excess  of 
ammonia  is  evaporated,  solution  of  silver  nitrate  is  added,  and  the 
whole  heated.  The  mixture  immediately  becomes  cloudy,  then 
blackens,  and  deposits  upon  the  sides  and  bottom  of  the  vessel  a  fine 
mirror  of  metallic  silver. 

If  hydrochloric  acid  be  really  present  in  a  sample  of  chloral,  it  is 
most  easily  detected  by  testing  the  aqueous  solution  with  silver 
nitrate,  which  will  at  once  produce  a  precipitate  or  turbidity. 

Chloral  hydrate  may  be  considered  pure  if  it  stands  the  following 
tests : — 

1.  It  .should  be  neutral  to  test  paper. 

2.  With  nitric  acid  it  should  not  give  off"  any  red  vapours. 

B.  Its  solution  ought  to  remain  clear  on  the  addition  of  silver 
nitrate. 

4.  "When  decomposed  by  caustic  potash  it  should  yield  72  2  per 
cent,  of  chloroform. 

The  Qualitative  Examination  of  Cinchona  and  Opium.  MM. 
Lepage  and  Patrouill  ard.   (Pharm.  Journ.,  Srd  series,  mu.,  795.) 

Cinchona. — Take  a  fraerment  from  several  barks  in  the  same  bundle 


PHARMACY.  279 

and  reduce  to  a  fine  powder;  suspend  1  gram  of  the  powder  in  10 
grams  of  distilled  water  containing  1  gram  of  dilute  sulphuric  acid, 
and  leave  them  in  contact  two  or  three  hours,  agitating  frequently. 
At  the  end  of  this  time  add  70  grams  of  distilled  water,  and  leave  in 
contact  several  hours  more,  still  taking  care  to  agitate  the  mixture 
frequently.  Then  allow  it  to  deposit,  and  afterwards  filter.  If  the 
cinchona  be  of  good  quality,  solution  of  the  double  iodide  of  cadmium 
and  potassium,  prepared  by  dissolving  2" 80  grams  of  iodide  of  cad- 
mium and  2'50  grams  of  iodide  of  potassium  in  50  grams  of  dis- 
tilled water,  when  poured  in  slight  excess  into  this  liquid,  should 
produce  at  once  an  abundant  turbidity,  resulting  after  some  hours 
in  a  voluminous  precipitate.  If  the  bark  contain  no  more  than  10 
or  12  parts  of  alkaloid  per  1000  the  reagent  does  not  give  rise  to 
any  turbidity,  or  at  most  to  a  slight  opacity.  The  yellow,  red,  and 
grey  barks  may  be  examined  in  this  manner. 

Opium. — Reduce  O'lO  gram  to  powder  in  a  glass  mortar,  and  sus- 
pend the  powder  in  25  grams  of  distilled  water ;  leave  the  mixture 
in  contact  during  half  an  hour,  agitating  occasionally,  and  then  filter. 
Take  two-thirds  of  this  liquor,  which  should  possess  a  markedly 
bitter  taste,  and  pour  into  it  some  drops  of  solution  of  iodide  of  cad- 
mium and  potassium.  If  the  opium  be  of  good  quality  an  abundant 
turbidity  is  produced,  to  which  rapidly  succeeds  a  flocculent  precipi- 
tate ;  whilst  if  it  contain  not  more  than  4  or  5  per  cent,  of  alkaloid 
or  less,  at  the  most  a  slight  turbidity  will  be  produced.  The  one- 
third  part  of  the  solution  that  is  reserved,  when  tested  with  very 
dilate  perchloride  of  iron  ought  to  acquire  a  decided  red  colour,  which 
is  the  reaction  characteristic  of  meconic  acid. 

The  Officinal  Wine  of  Guinine.  (Ghem.  and  Drugg.,  1877,  154.) 
Every  one  who  has  prepared  the  wine  according  to  the  Pharmacopoeia 
formula  must  have  noticed  immediately  after  eSecting  solution  of 
the  quinine  the  formation  of  a  brown  flocculent  precipitate,  varying 
probably  with  different  orange  wines  somewhat  in  quantity,  but 
always  considerable  and  always  of  the  same  appearance.  The  pre- 
cipitate is  annoying,  especially  to  makers  of  large  quantities  of  the 
wine,  as  it  both  necessitates  filtration  and  renders  the  process  tedious. 
Moreover,  a  second  deposit  after  a  time  almost  invariably  again 
forms,  which,  although  smaller  in  quantity,  is  even  more  trouble- 
some if  it  appears,  as  very  probably  it  may,  after  the  preparation 
has  been  bottled  and  stored. 

To  determine  the  nature,  cause,  and  extent  of  this  precipitate,  a 
series  of  investigations  were  undertaken,  the  result  of  which  may  be 
briefly  summarised  as  follows  : — 


280  YEAR-BOOK    OF    PHARMACY. 

1.  The  precipitate  was  found  to  be  principally  tannate  of  quinine, 
along  with  extractive  and  colouring  matters. 

2.  The  quinine  recovered  from  the  deposit  varied  in  quantity,  but 
was  frequently  found  to  form  a  large  percentage  of  the  quinine 
originally  added  to  the  wine. 

3.  The  deposit  continued  to  form  so  long  as  any  tannin  was  found 
to  exist  in  the  wine,  after  which  the  addition  to  any  extent  of  more 
quinine  and  citric  acid  gave  no  further  precipitate. 

The  raisins  from  which  the  wine  is  generally  fermented  were  at 
first  suspected  as  being  the  primary  cause  of  the  presence  of  the 
tannin ;  but  from  further  inquiries  it  was  ascertained  that  tannin  is 
veiy  generally  employed  to  clarify  the  wine  in  certain  stages  of  the 
process  of  fermentation,  and  that  the  excess  of  tannin  thus  added 
is  afterwards  removed  from  the  wine  by  the  addition  of  isin- 
glass. 

This  process,  even  where  carefully  conducted,  seems  at  the  best  to 
partake  a  good  deal  of  the  rule  of  thumb  procedure,  the  principal 
care  apparently  being  not  to  add  too  much  of  the  isinglass,  excess  of 
which  in  the  wine  is  in  some  respects  even  more  objectionable  than 
the  tannin.  Of  many  plans  which,  have  been  tried  to  rid  the  wine 
of  the  superfluous  tannin,  none  have  been  altogether  successful  which 
have  not  in  some  way  or  another  been  objectionable.  Even  when 
honestly  prepared,  which  we  are  sorry  to  say  it  very  seldom  is,  it  is 
apparent  that  the  quinine  which  it  contains  must  ultimately  be  an 
unknown  factor,  whilst  it  has  this  further  serious  objection,  that  in 
too  many  instances  it  contains  also  an  unknown  quantity  of  alcohol. 
The  Pharmacopoeia  states  that  it  contains  about  12  per  cent. ;  but 
this  will  be  found  insnflEicient  to  keep  it  from  decomposition,  and  as 
a  matter  of  fact  most  commercial  orange  wines  contain  double  this 
percentage  of  alcohol,  and  in  some  instances  more,  thus  exceeding  in 
strength  even  a  fortified  sherry. 

Poisonous  Properties  of  Glycerin.  MM.  Dujardin  Beaumetz 
and  Audige.  (From  Bull,  general  de  Therap.)  The  authors  have 
studied  the  effects  on  dogs  of  large  doses  of  glycerin  hypodermically 
injected,  and  have  arrived  at  the  following  conclusions  : — 

1.  Pure  glycerin  injected  in  the  proportion  of  8  to  10  grams  for 
each  kilogram  of  the  weight  of  the  animal  produces  death  within 
twenty-four  hours. 

2.  The  symptoms  produced  arc  analogous  to  those  of  acute  alco- 
holism. 

3.  The  microscopic  lesions  are  similar  to  those  in  alcoholism. 

4.  From  a  therapeutic  point  of  view  it  should  therefore  be  under- 


PHARMACY.  281 

stood  that  the  administration  of  large  doses  of  glycerin  may  be 
attended  with  danger. 

The  Alterability  of  Calomel  under  various  Influences,  and  the 
Precautions  necessary  in  its  Therapeutic  Employment.  M.  Jolly  . 
(Chem.  and  Drugg.,  from  Gazette  Medicale.)  Owing  to  the  report 
which  appeared  in  the  Italian  pharmaceutical  papers,  on  the  forma- 
tion of  corrosive  sublimate  in  a  mixture  of  calomel  and  sugar,  the 
president  of  the  Society  of  Practical  Medicine  engaged  the  author 
to  make  some  experiments  to  clear  up  all  doubt  on  this  subject. 

Calomel  has  a  decided  tendency  to  decompose  into  mercury  and 
corrosive  sublimate,  and  many  physical  and  chemical  agents  facili- 
tate this  decomposition.  The  author  has  investigated  the  action  of 
these  various  agents,  and  embodies  his  results  in  the  following 
summary. 

Heat  always  causes  decomposition  to  a  greater  or  less  extent. 
Perfectly  pure  and  dry  calomel,  sublimed  alone,  takes  a  greyish 
tinge  from  the  liberation  of  metallic  mercury. 

Light  causes  the  change  into  mercury  and  corrosive  sublimate  to 
take  place  rapidly,  as  evidenced  by  the  change  in  colour. 

Oue  gram  of  calomel  digested  with  100  c.c.  of  a  2  per  mille 
solution  of  hydrochloric  acid  for  six  hours,  at  a  temperature  of  104° 
Fahr.,  yielded  3  milligrams  of  corrosive  sublimate. 

The  same  quantity  digested  with  5  per  mille  solution  of  sodium 
chloride,  yielded  at  the  end  of  six  hours  1  milligram  of  sublimate. 

A  2  per  cent,  solution  of  citric  acid  (to  represent  fruit  preserves, 
in  which  calomel  is  often  administered)  caused  the  production  of 
1  milligram  of  sublimate. 

The  hydrochloric  acid  and  sodium  chloride  represent  the  gastric 
juice.  When  calomel  passes  into  the  intestines,  it  comes  in  contact 
with  the  alkaline  secretions  of  the  bowels. 

A  half  per  cent,  solution  of  sodic  hydrate,  after  digestion  for  six 
hours  at  104°  Fahr.  with  one  gram  of  calomel,  gave  rise  to  6  milli- 
grams of  corrosive  sublimate. 

Under  similar  circumstance  a  1  per  cent,  solution  of  sodic  car- 
bonate gave  rise  to  4  milligrams,  and  a  1  per  cent,  solution  of 
calcined  magnesia  to  3  milligrams,  of  mercuric  chloinde.  1  gram 
each  calcined  magnesia  and  calomel  were  mixed,  and  at  the  end  of 
twenty- four  hours  were  treated  with  distilled  water  ;  1  milligram  of 
sublimate  was  found.  Lime  acts  like  magnesia.  Neither  carbonate 
of  lime  nor  magnesia  had  the  least  effect  at  the  end  of  six  hours. 

From  these  experiments  the  author  draws  the  conclusion  that 
calomel  when  used  therapeutically  must  not  be  mixed  with  inferior 


282  YEAR-BOOK    OF    PHARMACY. 

sugars,  wliicli  are  always  acid  or  alkaline,  nor  with  the  alkaline 
chlorides  and  earths,  solutions  containing  alkaline  hydrates  or  car- 
bonates, or  mineral  or  vegetal)le  acids. 

The  Action  of  certain  Manipulations  and  Reagents  on  Calomel. 
F.  M.  Corwin.  (From  athesis  presented  to  the  Now  York  College 
of  Pharmacy  :  Nerv  E.emedies,  1877,  211.)  The  mercurous  chloride, 
or  calomel,  is  mild  in  its  action  on  the  human  system,  being  a  safe 
and  much -used  remedy. 

The  mercuric  chloride,  and  mercuric  salts  in  general,  are  power- 
ful and  corrosive  agents,  often  producing  serious  and  fatal  results. 

The  object  of  the  following  experiments  was  to  ascertain  whether 
mercuric  salts  were  produced  from  mercurmis  (namely  calomel)  by 
the  agents  and  methods  described. 

The  agents  were  either  physical  or  chemical. 

The  physical  agents  were  trituration,  boiling  with  water,  and 
sublimation. 

The  chemical  agents  were  certain  dilute  acids  and  salts  of  the 
U.  S.  P. 

The  tests  used  for  the  detection  and  identification  of  mei'curic 
mercury  w^ere  metallic  copper  and  hydrosulphuric  acid  in  strongly 
acidified  solutions. 

In  all  cases  where  a  deposit  was  obtained  on  copper,  the  copper, 
after  being  thoroughly  washed  and  dried,  was  placed  in  a  clean  dry 
test-tube  and  heated  to  redness. 

If  mercury  was  present  it  sublimed  and  collected  in  a  cooler  part 
of  the  tube.  A  crystal  of  iodine  was  then  placed  in  contact  with 
it,  and  heat  again  applied,  when  the  yellow  iodine  of  mercury  turn- 
ing red  by  friction  sublimed  in  another  part  of  the  tube. 

The  hydrosulphuric  acid  was  added  in  small  portions  at  a  time, 
producing  at  first  a  light  coloured  precipitate,  turning  yellow, 
orange,  brown,  and  black  as  the  snccessive  portions  were  added. 
This  reaction  is  characteristic  of  a  mercuric  salt. 

Several  attempts  to  obtain  absolutely  pure  calomel  proved  un- 
successful. That  used,  being  the  purest  which  was  examined,  was 
found  to  contain  a  small  quantity  of  ferric  iron,  probably  as  ferric 
chloride. 

1.  Physical  Agents. — a.  Trituration. — About  two  drams  of 
calomel  were  rubbed  in  'a  dry  porcelain  mortar.  On  moving  the 
pestle  through  it  with  pressure  it  produced  shining  straw  yellovj 
streaks,  and  the  Avhole  powder  gradually  assumed  a  yellowish  tint. 
After  rubbing  for  half  an  hour  it  was  macerated  with  water,  filtered, 
and  the  filtrate  acidified  with  hydrochloric  acid. 


PHARMACY. 


283 


Copper  :  no  action.     Hydrosulphuric  acid  :  no  action. 

b.  Boilimj. — 1.  About  two  drams  were  heated  in  a  flask  with 
water,  on  a  water  batli,  for  fifteen  minutes,  the  mixture  filtered,  the 
filtrate  evaporated  about  one-half  on  a  water  bath,  and  acidified 
with  hydrochloric  acid. 

Copper  :  no  action.     Hydrosulphuric  acid :  no  action. 

2.  About  two  drams  were  boiled  in  a  flask  with  water  by  direct 
contact  with  flame,  and  under  constant  agitation,  for  fifteen  minutes  ; 
filtered,  the  filtrate  evaporated  about  one-half  on  a  water  bath,  and 
acidified  with  hydrochloric  acid. 

Copper:  a  deposit.    Hydrosulphuric  acid  :  character  istic  precipitate. 

c.  Sublimation. — 1.  About  twenty  grains  were  heated  in  a  dry 
test-tube,  the  heat  being  only  sufficient  to  slowly  sublime  it.  It 
was  then  macerated  with  a  small  quantity  of  water,  filtered,  the 
filtrate  acidified  with  hydrochloric  acid. 

Copper  :  no  action.     Hydrosulphuric  acid  :  no  action. 

The  sublimate  was  perfectly  white. 

2.  About  twenty  grains  were  heated  so  as  to  sublime  rapidly,  the 
glass  becoming  red  hot.  It  w^as  macerated  with  water,  filtered,  and 
the  filtrate  acidified  with  hydrochloric  acid. 

Copper:  a  deposit.    Hydrosulphuric  acid  :  characteristic  precipitate. 

The  sublimate  had  a  greyish  appearance  in  places,  probably  due 
to  metallic  mercury. 

II.  Chemical  Agents. — a.  Acids. — The  acids  used  were  the  dilate 
acids  of  the  U.S.  Pharmacopoeia.  About  a  dram  of  calomel  was  placed 
in  a  five-inch  test  tube,  the  tube  was  nearly  filled  with  an  acid, 
and  allowed  to  macerate  for  three  days,  being  agitated  occasionally. 
It  was  then  filtered  and  the  filtrate  evaporated  about  one-half  on  a 
water  bath. 

With  some  acids  a  change  was  noted  in  the  appearance  of  the 
calomel ;  with  others  it  remained  unaltered.  The  following  table 
exhibits  the  results  : — 


Acids. 

Copper. 

Hydrosulphuric  Acid. 

Appearance. 

Hydrochloric    .     . 

Deposit 

Characteristic  ppt. 

Unchanged. 

Nitric 

Not  used 

>i                        n 

J, 

Sulphuric     .     .     . 

No  action 

No  action 

,, 

Hydrocyanic     .     . 

Deposit 

Characteristic  ppt. 

Turns  dark.* 

Nitro-hydrochloric 

Not  used 

)>                            u 

Unchanged. 

Phosphoric  .     .     . 

No  action 

No  action 

»i 

*  On  the  reaction  between  calomel  and  hydrocyanic  acid,  see  a  paper   by 
T.  H.  Powell  and  J.  Bayne,  in  Year-Book  of  Pharmacy,  1876,  372. 


28i 


YEAR-BOOK    OF    PHARMACY. 


b.  Sails. — Of  the  salts  used,  sixteen  were  in  solution  with  water. 
The  soliitious  were  made  by  dissolving  1  part  of  the  salt  in  10 
parts  of  water,  with  one  exception,  namely,  the  potass ic  chlorate 
solution,  which  was  made  by  dissolving  1  part  of  the  salt  in  20 
parts  of  water. 

About  half  a  dram  of  calomel  was  placed  in  a  five-inch  test  tube, 
the  tube  nearly  filled  with  a  solution  and  allowed  to  macerate  three 
days  with  occasional  agitation.  It  was  then  filtered,  and  the  filtrate 
acidified  with  hydrochloric,  nitric,  or  sulphuric  acid,  according  to 
the  character  of  the  salt. 

With  some  of  the  solutions  a  change  was  noted  in  the  appearance 
of  the  calomel,  either  immediately  or  on  standing. 


Solution  of 

Copper. 

Hydrosulph.  Acid. 

Appearance. 

Potass.  Bromide    .     . 

Deposit 

Characteristic  ppt. 

Lead  colour. 

„       Chlorate    .     . 

No  action 

No  action 

Unchanged. 

„       Cyanide     .     . 

Deposit 

Characteristic  ppt. 

Dark,  nearly  hlack. 

,,       Hypopliosphite 

No  action 

No  action 

Unchanged. 

,,       Nitrate.     .     . 

,, 

,j 

,,       Sulphate   .     , 

,, 

,, 

,, 

,,        Siilphite    .     . 

)» 

No  ppt.  Separation 
of  S. 

Greenish  grey. 

Pot.  and  Sod.  Tartrate 

Deposit 

Characteristic  ppt. 

Unchanged. 

Ammon.  Bromide,.     , 

))                )> 

Slate  colour. 

,,         Chloride  .     . 

11                                       M 

Unchanged. 

„         Iodide      .     . 

,1 

Orange     red    ppt., 

Turns  yellow,  then 

which    gradually 

dark  with   green 

turns  dark,  same 

tint.     Solutionis 

as      Hg  CL      in 

yellow. 

NHJ 

Nitrate 

" 

Characteristic  ppt. 

Dark    at  point    of 
contact.        Grey 
on  agitating. 

,,        Sulphate.    . 

,, 

11                                    1! 

Unchanged. 

Sodic  Chloride  .     .     . 

,, 

i>                )> 

Ferric        ,, 

No  action 

No  action 

,, 

„     Pyrophosphate  . 

'• 

" 

Of  the  two  following  salts,  about  a  dram  of  each  was  rubbed, 
with  an  equal  bulk  of  calomel,  in  a  porcelain  mortar  for  fifteen 
minutes.  They  were  then  macerated  with  a  small  quantity  of  water, 
filtered,  and  the  filtrates  acidified. 


Filtrate  from 

Copper. 

Hydrosulphuric  Acid. 

Bismuth  Subnitrate     . 
Ferric  Ferrocyanide 

No  action 

Peculiar  ppt.     Not    characteristic    of 

mercury. 
No  action. 

PHARMACY.  285 

Note  on  a  Test  for  Alcohol. — Dr.H.  Hager.  (Pharm.  Cen- 
tralhalle,  1877,  154.)  A  solution  of  1  part  of  molybdic  acid  in 
10  parts  of  strong  sulphuric  acid  has  been  recommended  as  a  test 
for  ethyl  alcohol  and  other  alcohols.  In  a  more  concentrated  form 
the  same  reagent  has  been  in  use  for  some  time  as  a  test  for 
morphine  (Frdhde's  test),  and  has  since  its  introduction  for  this 
purpose  been  applied  to  a  good  many  other  substances  possessing 
the  properties  of  reducing  agents.  For  its  application  as  a  test  for 
alcohol,  Davy  recommends  the  following  precautions : — Three  to 
four  drops  of  the  reagent  should  be  gently  heated  in  a  porcelain 
capsule,  and  one  or  two  drops  of  the  liquid  to  be  tested  then  added ; 
if  the  latter  is  likely  to  contain  but  a  very  small  proportion  of 
alcohol,  the  mixture  should  be  warmed  in  a  water  bath. 

Following  these  directions  the  author  has  repeatedly  tried  the 
test,  but  has  failed  to  obtain  the  reaction. 

Practical  Hints  about  Dialysis. — (New  Bemedies,  1877,  229.) 
Dialysis  is  a  species  of  osmosis,  that  is,  a  diffusion  or  passage  of 
fluids  through  organic  membranes.  The  late  Thomas  Graham,  to 
whom  we  are  indebted  for  the  first  knowledge  of  the  law  of  diffu- 
sion, divides  bodies,  in  respect  to  their  diflPusibility,  into  two  classes  : 
one  of  these  he  termed  crystalloids,  being  mostly  crystallizable  sub- 
stances, or  closely  approaching  them  in  character.  They  have  a 
strong  affinity  for  their  solvents,  and  retard  the  evaporation  of  the 
latter  by  their  presence.  The  other  class  he  denominated  colloids, 
which  are  uncrystallizable,  of  a  glassy  or  horny  structure  when  dry 
(like  gelatine,  etc.),  and  generally  of  an  insipid  taste. 

These  two  classes  of  bodies  may  be  almost  entirely  separated 
from  each  other  by  placing  the  mixture  containing  them  on  one 
side  of  an  organic  membrane  which  is  in  contact  with  water  on  the 
other.  A  double  osmosis  then  takes  place ;  from  one  side  the 
crystalloids  pass  through  the  membranes  into  the  water,  and  from 
the  other  side  water  passes  into  the  mixture.  The  ratio  of  diS'usion 
is  inversely  proportional  to  the  densities  of  the  liquids  on  either 
side  :  a  dense  liquid  will  pass  slowly ;  a  dilute  liquid,  or  pui^e  water, 
more  rapidly.  The  colloid  substances,  however,  are  not  absolutely 
retained  on  one  side  ;  they  also  pass  through  the  membrane,  but  at 
so  slow  a  rate  that  the  crystalloids  may  nearly  all  have  penetrated 
the  membrane  before  an  appreciable  amount  of  colloids  has  accom- 
panied them. 

The  apparatus  employed  for  this  process  is  genei"ally  constructed 
in  the  following  manner : — A  light  hoop  of  wood,  or  of  gutta  percha, 
or  better,  of  glass,  about  2  inches  deep  and  5-10  inches  in  diameter, 


286  YEAR-BOOK   OF    PHARMACY. 

is  covered  with  a  piece  of  moistened  bladder  or  parcliment-paper — 
which  have  been  found  in  practice  to  be  the  most  suitable  mem- 
branes for  this  purpose — so  as  to  form  a  sieve-like  vessel.  The  disk 
of  bladder  or  parchment-paper  should  be  considerably  larger  in 
diameter  than  the  hoop,  and  it  should  be  bound  to  the  latter  by  a 
string,  or  by  another  hoop  of  similar  material.  The  membrane 
must  be  entirely  free  from  rents  or  pin-holes,  which  may  be  as- 
certained by  sponging  one  side  with  water,  and  observing  whether 
any  wet  spots  appear  on  the  other  side.  In  the  latter  case,  the 
defects  may  sometimes  be  remedied  by  applying  liquid  albumen, 
and  coagulating  it  by  heat.  Broad  glass  shades,  or  lamp-chimneys, 
or  similar  articles,  may  also  be  used.  In  absence  of  these,  a  funnel, 
the  neck  of  which  is  broken  oflF,  may  answer ;  only  in  this  case  the 
membrane  is  placed  inside  of  it,  folded  in  the  form  of  a  star-filter. 
The  apparatus  then,  prepared  in  any  of  these  ways,  is  called  the 
diahjser. 

This  is  floated  upon  a  quantity  of  pure  water  contained  in  an- 
other larger  vessel,  which  has  received  the  name  cxarysator.  The 
size  of  the  latter  and  the  amount  of  water  contained  in  it  depend 
upon  the  object  to  be  accomplished.  If  the  colloid  substance  re- 
maining in  the  dialyser  be  our  chief  object,  it  is  best  to  employ  a 
large  quantity  of  water  at  once ;  the  crystalloid  bodies  pass  into 
this  in  the  form  of  a  dense  solution,  which  sinks  to  the  bottom  and 
causes  the  lighter  unsaturated  water  to  be  constantly  pushed  up 
towards  the  membrane.  If  we,  however,  want  to  separate  the 
crystalloids,  to  the  neglect  of  the  colloids,  we  must  use  as  small  a 
quantity  of  water  as  possible. 

The  liquid  to  be  dialysed  is  poured  into  the  dialyser  to  the  height 
of  about  one-half  inch,  or  a  little  more,  but  never  to  exceed  one- 
fourth  of  its  depth,  and  the  apparatus  then  floated  on  the  w^ater  in 
the  exarysator.  The  best  way  is  to  introduce  just  as  much  liquid 
into  the  dialyser  as  will  cause  the  latter  to  sink  into  the  water  to 
one-third  of  the  height  of  the  contained  liquid.  These  precautions 
are  necessitated  by  the  fact  that  water  will  difi'use  upwards  into  the 
dialyser  more  rapidly  than  the  crystalloids  will  pass  through  the 
other  way ;  and  this  is  more  particularly  the  case  when  bladder  is 
used.  The  solution  of  crystalloids  produced  in  the  surrounding 
water  is  called  diffusate.  In  most  cases  the  difiusiun  may  be  greatly 
accelerated  by  the  application  of  a  gentle  heat. 


NOTES    AND    FORMULA. 


PART  ly. 

NOTES   AND    FORMULA. 

A  New  Process  for  the  Estimation  of  Chicory  in  Coffee.  A. 
Smith.  (Chemical  News,  34,  1876,  283.)  Take  5  grams  of  the 
coffee,  and  pour  upon  it  about  25  c.c.  of  boiling  water,  and  filter  ; 
then  pour  it  into  a  Nessler  tube,  and  add  acetate  of  lead,  which  will 
throw  down  the  colouring  matter  of  the  coffee,  but  leave  that  of 
the  chicory,  which  can  then  be  estimated  by  comparing  it  with  a 
standard  of  a  known  quantity  of  chicory. 

The  Presence  in  Beer  of  a  Substance  Resembling  Colchicine. 
H.  van  Greldern.  (Archiv  der  Pharm.,  July,  1876.)  E.  Danue- 
berg  stated  recently  that  he  had  obtained  from  beer  an  alkaloid  re- 
sembling colchicine  in  its  reactions  (Archiv  der  Pharm.,  May,  1876.) 
The  writer  has  obtained  the  same  body,  in  1874,  by  the  method  of 
Stas  and  Otto,  and  found  then  that  it  could  also  be  obtained  from  a 
mixture  of  unadulterated  hops  and  gelatin.  The  latter  body  is 
always  present  in  beer,  and  is  possibly  the  cause  of  the  precipitate 
formed  with  the  general  reagents  for  alkaloids,  and  which  are  not 
produced  if  pure  hops  alone  be  employed  for  the  experiment. 

A  Spurious  Beeswax.  (New  Remedies,  from  Pharm.  Post.)  In 
appearance,  colour,  fracture,  brittleness,  pliability,  and  odour  (on 
the  outside  portions),  this  pseudo-wax  could  scarcely  be  distinguished 
from  the  genuine.  But  the  freshly-cut  surfaces  had  a  lustre  differ- 
ent from  that  of  true  wax,  and  on  breaking  the  mass  into  pieces  a 
distinct  odour  of  resin  was  perceptible.  On  melting  it  with  a  gentle 
heat,  the  honey  odour  disappeared  entirely,  but  the  pitchy  odour 
became  gradually  more  intense  and  oppressive.  These  simple  means 
having  already  pointed  out  the  probable  composition,  the  melting 
point  and  the  specific  gravity  were  determined  in  the  following 
manner  : — A  wide-necked  glass  flask  was  filled  three-fourths  with 
water,  and  into  the  middle  of  this  was  immersed  a  thermometer  and 
a  test-tube  containing  some  fragments  of  the  wax ;  the  mouth 
having  been  loosely  stoppered,  heat  was  carefully  applied,  until 
about  one-third  of  the  wax  had  melted.  The  temperature  at  this 
point  was  70°  C.  (158°  F.),     To  determine  the  specific  gravity,  two 

U 


290  YEAK-BOOK   OF    PHARMACY. 

equally  large  pieces  were  dropped  into  a  beaker  containing  dilute 
alcohol,  in  •wbicli  they  sank  ;  distilled  water  was  now  gradually 
added  until,  after  stirring,  the  pieces  floated  a  little  below  the  level 
of  the  liquid.  The  speci6c  gravity  of  the  latter,  being  found  to  be 
0  562,  corresponds  to  that  of  the  wax.  One  gram  of  the  sub- 
stance was  warmed  in  a  small  flask  with  10  grams  of  chloroform. 
The  solution  was  clear  and  yellow,  but  in  cooling  became  opaque, 
and  deposited  on  the  sides  an  almost  transparent  and  colourless 
mass.  Another  gram  was  dissolved  by  heat  in  15  grams  of  70 
per  cent,  alcohol,  and  set  aside  to  cool.  This  caused  the  deposition 
of  globular  colourless  masses,  leaving  the  liquid  of  a  clear  yellow 
colour.  The  globules  having  been  separated  by  filtration,  they  were 
dried  and  "weighed.  They  amounted  to  0  6  gram,  and  had  a  spe- 
cific gravity  of  0"910.  The  filtrate,  on  evaporation,  left  behind  a 
brittle,  yellow  resin,  weighing  nearly  0"4  gram.  One  gram  of 
shavings  was  next  boiled  in  a  solution  of  1"4  gram  of  borax  in 
20  grams  of  distilled  water,  whereby  a  colourless  mass  was  ob- 
tained, floating  on  the  top  of  the  liquid,  which  latter  was  cloudy, 
but  did  not  become  either  milky  or  gelatinous  on  cooling.  Japan 
wax  was  therefore  not  present.  Another  portion,  in  fine  shavings. 
was  shaken  with  dilute  ammonia  ;  but  the  liquid  remained  clear  and 
transparent,  and  the  substance  unaltered,  which  proved  the  absence 
of  stearine  as  -well  as  tumeric  and  Orleans.  The  above-mentioned 
srlobular  masses,  free  from  resin,  were  now  examined  for  parafQn. 
They  had  a  lustrous,  alabaster-like  appearance,  became  soft  on 
kneading,  -without  getting  adhesive,  and  dissolved  easily  and  com- 
pletely in  oil  of  turpentine  and  benzin,  but  were  entirely  insoluble  in 
five  parts  of  hot  absolute  alcohol.  They  were  hence  pure  paraffin. 
The  composition  of  the  substance  was  therefore  60  parts  of  paraffin, 
and  40  parts  of  yellow  resin,  covered  with  a  thin  coating  of  genuine 
beeswax.  The  specific  gravity  in  this  case  was  identical  with  that 
of  many  .samples  of  genuine  beeswax. 

Koumiss  Extract.     (Zeitschrift  des  oesterr.  Apoih.  Ver.,  1876,  526.) 
The  following  formula  yields  a  good  preparation  : — 

Powdered  Sugar  of  Milk       .        .        .  100  parts. 

Glucose  (prepared  from  starch)    .         .  100     ,, 

Cane  Sugar 300     „ 

Bicarbonate  of  Potassium     .        .         .  36     ,, 

Common  Salt 33     ,, 

Di.sRolve  these  ingredients   in  600  parts  of  boiling  fresh  whey  of 
milk,  allow  the  solution  to  cool,  then  add  100  parts  of  rectified  spirit, 


NOTES   AND    FORMULA.  291 

and  afterwards  100  parts  of  strained  fresh  beer  yeast.  Stir  the  mix- 
tui'e  well,  and  put  it  ioto  bottles  containing  a  quarter  of  a  litre  each, 
The  bottles  must  be  well  corked  and  kept  in  a  cool  place. 

For  the  preparation  of  koumiss  add  5  to  6  tablespoonfuls  of  this 
extract  to  a  litre  of  skimmed,  lukewarm  milk  contained  in  a  bottle 
of  thick  glass  ;  cork  well,  keep  the  bottle  for  half  a  day  in  a  moder- 
ately warm  room  (at  16°-20°  C),  and  afterwards  in  a  cool  cellar, 
shaking  occasionally.  The  bottle  should  be  filled  to  within  3-4 
centimetres  of  the  cork.  After  two  days  the  koumiss  is  ready  for 
use. 

Poisonous  Materials  in  Hair  Dyes.  (The  Lancet,  January  13th, 
1877.)  Out  of  twenty-one  examples  of  so-called  hair  restorers, 
including  all  the  best  known,  examined,  no  less  than  fourteen  were 
practically  identical  in  their  nature.  They  contained  sulphur  in 
suspension,  and  also  lead  in  varying,  but  always  in  very  considerable, 
quantity.  Three  of  these  preparations  bore  American  labels,  the 
rest  were  English.  The  descriptions  varied  a  good  deal.  Only  one 
was  plainly  described  on  the  label  as  poisonous  if  taken  internally, 
while  many  were  described  as  "perfectly  harmless,"  "free  from 
injurious  substances,"  and  so  on.  The  prices  varied  from  Is.  to  Qs. 
per  bottle. 

Two  more  samples,  one  of  them  American,  were  found  to  contain 
lead  and  sulphur,  but  in  a  different  form.  The  sulphur  was  present 
as  hyposulphide ;  and  in  fact,  these  preparations  may  be  substan- 
tially imitated  by  adding  hyposulphide  of  soda  to  a  solution  of  a 
lead  salt.  A  white  precipitate  first  appears,  which  dissolves  in 
excess,  and  the  solution  so  obtained  does  not  give  a  preci'pitate  loith 
iodide  of  potassiiuii.  This  is  noteworthy,  because  in  the  handbill 
which  accompanies  one  of  the  samples  purchasers  are  warned 
against  the  dangerous  hair  preparations  which  contain  lead,  as 
likely  to  lead  to  paralysis  of  the  brain  and  insanity,  and  are  directed 
to  test  all  preparations  with  iodide  of  i)otassium. 

In  another  sample,  an  American  one,  no  free  or  loosely  combined 
sulphur  was  found,  but  only  lead  in  considerable  quantity.  Another 
of  the  preparations  was  contained  in  two  bottles,  in  one  of  which 
ammonio-nitrate  of  silver,  and  in  the  other  pyrogallic  acid  was 
detected.  This,  therefore,  belongs  to  an  entirely  different  class 
from  the  preceding. 

The  remaining  three  preparations  analysed  were  intended  for 
lightening,  instead  of  darkening,  the  colour  of  the  hair.  No  sub- 
stantial difference  between  these  samples  was  detected.  Each  was 
found  to  contain  a  tolerably  concentrated  and  slightly  acidulated 


202  YEAR-BOOK    OF    PHARMACY. 

Bolntion  of  peroxide  of  hydrogen.  It  is  well  known  that  this  is  the 
active  agent  in  preparations  of  this  kind.  It  can  hardly  be  con- 
sidered as  poisonous,  but  its  action  on  the  hair  is  said  to  be 
injurious.  The  silly  fashion  which  prompted  its  use  is,  the  authors 
believe,  dying  out. 

It  will  be  seen  that,  out  of  the  twenty-one  samples  examined,  no 
less  than  seventeen  contained  lead.  This  lead  was  present,  it  must 
be  remembered,  not  as  a  mere  trace,  but  in  most  cases  in  large  and 
deleterious  quantity.  In  one  sample,  and  that  not  the  worst,  was 
found  five  grains  and  a  half  of  lead  (equivalent  to  about  10  grains 
of  crystallized  sugar  of  lead)  in  each  fluid  ounce  of  the  liquid. 

A  subsidiary  question  arises  out  of  this  inquiry  which  deserves 
the  most  careful  consideration  of  the  medical  profession.  Is  it  not 
possible  that  lead  poisoning  may  sometimes  be  produced  by  the 
incautious  use  of  these  preparations  ?  Evidence  upon  the  point  is 
conflicting,  and  many  physiologists  hold  that  such  an  absorption 
through  the  scalp  cannot  take  place  unless  the  skin  is  broken. 
Taylor  quotes  a  case  to  the  contrary  which  came  within  his  own 
observation,  and  many  others  of  the  same  kind  have  been  noticed. 
But  few,  if  any,  of  these  cases  are  definitive,  and  real  proof 
appears  still  to  be  lacking.  It  is,  perhaps,  not  likely  that  such 
poisoning  commonly  occurs,  if  it  ever  does.  In  the  majority 
of  instances  the  liquid  would  probably  be  used  with  a  certain 
amount  of  discretion,  and  would  be  applied  mainly  to  the  hair 
rather  than  to  the  head.  But  if  the  preparation  were  used  incau- 
tiously, if  the  lead  solution  were  rubbed  frequently  and  in  consider- 
able quantity  into  the  skin  of  the  head,  there  would  be  danger, 
especially  if  the  skin  were  broken. 

Many  recorded  cases  show  that  very  minute  quantities  of  lead 
may  after  a  time  produce  symptoms  of  poisoning.  Certain  circum- 
stances, moreover,  induce  the  authors  to  think  that  incipient  lead 
poisoning  is  more  common  than  is  generally  suppo.sed.  In  all 
chemical  laboratories  the  testing  for  lead  in  drinking  water  is  a 
common  experience.  The  number  of  samples  of  water  sent  for  this 
purpose  is  surprising.  Now,  in  a  great  many  instances  no  lead  is 
found  ;  and  it  is  worthy  of  consideration,  whether  in  some  of  these 
cases  the  symptoms  which  threw  suspicion  unjustly  on  the  water 
may  not  have  been  caused  by  the  use  of  lead  cosmetics. 

Regeneration  of  Spent  Albumen  by  Means  of  Pepsin.  J.  "Wagner 
and  G.  Witz.  (Journ.  Cliem.  Soc,  Aug.,  18~G,  from  Dinrjl.  polyt. 
Journ.,  ccxix.,  166.)  The  property  of  an  aqueous  solution  of  albumen 
to  deposit  the  albumen  in  the  insoluble  form  on  aj^plicatiou  of  heat. 


NOTES    AND    FORMOLj;.  293 

is  applied  to  the  fixing  of  a  variety  of  important  colours  upon 
cotton.  Both  soluble  and  insoluble  colours  are  mixed  with  the  cold 
solution,  printed  on  the  cotton  piece,  and  the  latter  is  then  steamed, 
which  converts  the  soluble  albumen  into  the  insoluble  variety, 
forming  a  kind  of  fixed  and  elastic  varnish  upon  the  cloth,  and 
mechanically  fixing  the  colouring  matter.  Both  egg  and  blood 
albumen  pass  into  the  insoluble  form,  either  wliolhj  or  partially,  if  the 
temperature  of  the  drying  chamber  has  passed  35°,  or  even  if 
exposed  to  the  sun  accidentally,  or  after  allowing  it  to  stand  too 
long.  Now,  the  problem  has  been,  how  to  recover  albumen  which 
has  thus  become  insoluble  and  is  lost,  so  as  to  obtain  it  again  in  the 
soluble  form  for  further  service  ?  Dilate  alkaline  carbonates  or 
hydrates  could  bring  such  albumen  into  solution  again,  but  such  a 
solution  lacks  the  power  of  coagulating  on  application  of  heat ;  in 
fact,  the  constitution  of  the  albumen  is  altered  by  the  alkalies,  a 
portion  of  its  sulphur  being  abstracted,  and  the  substance  in  solu- 
tion is  therefore  not  albumen  at  all. 

This  prejudicial  action  of  alkalies  is  at  times  experienced  in 
working  ;  thus,  if  the  basic  lead  chromate  be  not  completely  freed  by 
washing  from  adhering  lime,  and  be  then  thickened  with  albumen 
and  printed,  the  bright  orange  is  not  obtained  on  the  cotton  on 
steaming,  but  through  presence  of  lead  sulphide,  a  muddy  brown. 

At  lensfth  J,  Wagner  devised  the  foUowino'  successful  method  : — 
He  brought  350  to  400  grams  of  such  unserviceable  albumen  into 
contact  with  30  grams  of  calf's  stomach,  cut  into  little  pieces  and 
distributed  through  1  litre  of  water.  The  water  was  treated  with 
10  grams  of  concentrated  hydrochloric  acid,  and  had  a  tempei-ature 
of  37'5°.  After  24  to  36  hours'  standing  the  whole  was  passed 
through  a  fine  sieve,  and  the  filtrate  neutralized  with  ammonia,  and 
thus  an  albumen  solution  was  obtained  which  answered  every 
purpose  completely.  Witz  uses  a  sheep's  stomach,  and  to  1  litre  of 
acidified  water  nearly  125  grams  of  dry  insoluble  albumen.  He 
states  that  pig's  stomachs  are  even  more  active  than  sheep's.  He 
further  digests  for  40  hours  at  a  temperature  of  35^  to  40°,  whereby 
somewhat  more  than  half  the  albumen  goes  into  solution.  The  dis- 
solved portion  being  separated  by  a  sieve,  the  insoluble  portion  is 
treated  once  more  with  acidified  water  in  the  same  manner,  to  bring 
a  further  portion  of  albumen  into  solution.  The  solution  so  obtained 
is  without  odour  and  but  little  coloui-ed,  a  fact  worthy  of  note  as 
regards  blood  albumen.  It  has  also  the  property,  after  neutraliza- 
tion by  ammonia,  to  become  coagulated  either  by  boiling  or  by 
addition  of  alcohol.     Experiments  as  to  the  use  of  this  albumen  in 


294  YEAR-BOOK   OP   PHARMACY. 

ultramarine  printing,  showed  that  on  steaming  a  pure  fast  blue  is 
obtainable,  unaffected  by  boiling  soap  solution.  There  is  one  reac- 
tion which  marks  a  difference  between  albumen  recovered  by  pepsin 
and  ordinary  albumen.  The  former  treated  with  acetic  acid,  before 
or  after  neutralization  with  ammonia,  either  does  not  at  all  become 
turbid,  or  only  slightly,  and  in  no  case  gelatinizes,  even  after  long 
standing.  On  the  conti-ary,  one  part  of  egg  albumen  dissolved  in  10 
parts  of  water,  so  that  the  filtered  solution  has  a  sp.  gr.  of  1'027, 
and  treated  with  an  equal  or  half  volume  of  acetic  acid  of  sp.  gr. 
I'OSO,  immediately  forms  a  solid  transparent  jelly.  This  also  takes 
place  if  hydrochloric  acid  be  added.  Witz  has  proved  conclusively 
that  under  no  circumstances  whatever  is  coagulated  albumen  soluble 
in  acetic  acid.  The  text-books  usually  state  that  albumen  solutions 
are  not  precipitated  at  all  by  acetic  acid ;  and  are  thus  in  great 
eiTor.  Digestion  with  pepsin  is  thus  a  certain  method  of  bringing 
coagulated  albumen  again  into  solution.  Just  as  cloth,  which  has 
undergone  some  injury  in  finishing,  may  be  quite  freed  from  its 
size  by  digestion  with  malt,  and  much  more  easily  than  by  long- 
treatment  with  boiling  water,  so  by  the  help  of  pepsin  printed 
albumen  colours,  even  after  steaming,  can  be  completely  removed 
from  the  fabric. 

For  this  purpose  the  piece  is  placed  in  warm,  slightly  acidified 
water,  together  with  some  pieces  of  the  membrane  of  a  calf's 
stomach.  The  pepsin  in  presence  of  the  dilute  acid  dissolves  the 
albumen,  and  the  colouring  matters,  as  chrome  green,  lampblack, 
chrome  yellow,  ultramarine,  ochre,  etc.,  are  now  readily  removed 
by  washing.  Pepsin  can  bring  about  the  solution  of  albumen  co- 
agulated by  boiling,  as  well  as  that  of  otherwise  insoluble  albumen ; 
but  the  two  solutions  differ,  as  the  former  will  not  coagulate  on 
boiling,  but  the  latter  will.  The  presence  of  a  small  quantity  of 
free  hydrochloric  acid  is  indispensable  in  aiding  the  solution  of  the 
albumen  by  the  pepsin.  Dilute  hydrochloric  acid  (1  part  of  sp.  gr. 
1*169  in  100  of  water)  alone,  after  some  days,  at  a  temperature  of 
38°,  can  effect  the  solution  of  insoluble  albumen.  The  solution  will 
coagulate  on  boiling,  and  answers  well  in  printing.  By  digesting 
blood- fibrin  in  dilute  hydrochloric  acid,  a  fibrin  solution  is  obtained, 
which  coagulates  on  boiling,  exactly  as  the  albumen  solution  above- 
mentioned  does.  It  is  thus  possible  that  fibrin  would  make  a  good 
substitute  for  egg  albumen.  Coagulated  fibrin,  like  albumen,  on 
treatment  with  acidified  pepsin  solution,  dissolves,  but  apparently 
in  an  altered  or  modified  form,  as  the  solution  will  not  coagulate 
on  boiling.     Coagulated  fibiin  can  also  be  dissolved  gradually  by 


NOTES   AND    FORMULAE.  295 

dilute  hydrochloric  acid  (1  part  of  sp.  gv.  1'169  to  100  of  water). 
On  heating  the  solution  precipitates  the  fibrin  as  a  thick,  solid  jelly. 
Mistura  Salicylica  Effervescens.    (Pharmaceut.  Goitralhalle,  187 7 
75.) 

^.     Acidi  Salicylic! 8,0  grams. 

Syrupi  Aurantii  corticis         .         .         .  30,0      ,, 

Aquffi  destillatae 207,0      ,, 

In  lagenam  immissis  adde 

Sodie  bicarbonatis  ....  5,0      „ 

lageuam  statim  obtui-audo.    Sepone  loco  frigido,  donee 
solutio  effecta  fuerit. 
Sign.    3SS  vel  51  singulis  vel  secundis  horis. 

Boli  Taenifugi.     (Pharmaceut.  Centralhalle,  1877,  76.) 

9,     Florum  Kosso 30,0  grams. 

Kamalae 15,0      ,, 

Extracti  Filicis  maris  aetherei         .         .  4,0      ,, 

Mellis  depurati        .         .         .         .         .  q.  s.       „ 

Misce.    Fiaut  boli  sexaginta. 

Coumarm  and  its  Uses.  L.  von.  Cotzhausen.  (Amer.  Journ. 
Pharm.,  Sept.,  1876,  405.)  In  preparing  coumarin  from  touka 
beans,  they  were  grated  and  exhausted  by  ether;  on  evaporating 
the  solvent,  crystals  of  coumarin,  rendered  impure  by  fatty  matter, 
were  obtained  and  purified  by  repeated  crystallization  from  alcohol. 
Sixteen  troy  ounces  of  tonka  yielded  117  grains  of  coumarin.  This 
is  the  process  of  Boullay  and  Boutron-Charlard.  A  somewhat 
smaller  amount  was  obtained  by  substituting  petroleum  benzin  for 
the  ether,  and  this  solvent  is  recomm.ended  as  being  more  eco- 
nomical. Coumarin  was  obtained  in  a  similar  manner  also  fi'om 
the  dried  herbs  of  Asperula  odorata,  Lin.,  Melilotus  officinalis,  Pers., 
Liatris  odoratissima,  Willd ,  and  Galium  triflonmi,  Mich. 

The  last-named  herb  is  frequently  collected  in  this  country  under 
the  supposition  that  it  is  the  Waldmeister  (Asperiola  odorata')  of 
Germany,  which  is  prepared  by  macerating  the  herb  in  a  cheap 
quality  of  Rhine  wine,  and  adding  sugar  and  a  few  drops  of  orange 
or  lemon  juice  to  suit  the  taste ;  cider  may  be  used  in  place  of 
wine.  Galium,  like  asperula,  belongs  to  the  order  Ruhiacece,  and  on 
drying  acquires  a  fragrant  odour,  due  to  coumarin,  and  contains 
also  an  astringent  principle,  a  yellow  resin,  a  fatty,  rather  un- 
pleasant oil,  and  grape  siigar. 

Coumarin  is  proposed  by  the  author  as  an  ingredient  in  the  fol- 
lowing preparations,  taking  the  place  of  tonka  beans  and  some  of 
the  herbs  mentioned  above  : — 


296  YEAR-BOOK    OP    PHARMACY. 

Exlr.  Nero  Mown  Hay. — Coumarin,  gr.  xij.  ;  essence  of  rose,  5SS. ; 
cologne  spirit,  ^ij. 

Exfr.  Mille  Fleurs. — Coumarin,  gr.  x. ;  oil  of  cinnamon,  gtt.  ij. ; 
oil  of  rose,  gtt.  iij . ;  oil  of  neroli,  gtt.  v. ;  oil  of  lemon,  gtt.  xv. ;  tinc- 
ture of  musk,  gr.  xv.;  tinct.  benzoin,  gtt.  xx.;  cologne  spirit,  3iij. 

Extr.  Tonquin  Music. — Musk,  gr.  x.;  cologne  spirit,  3iij.  Digest, 
filter,  and  add  oil  of  neroli,  gtt.  j.;  coumarin,  gr.  xij.;  extract  of 
vanilla,  5ij. 

Fltcid  Extract  of  Tonl-a. — Digest  tonka,  ^viij.,  with  strong  alco- 
hol, reserve  the  first  six  fluid  ounces,  evaporate  the  remainder  to 
two  fluid  ounces,  and  mix. 

Sachet  Mille  Fleurs. — Tonka,  3J . ;  vanilla,  5iij . ;  cinnamon  and 
cloves,  each  5iv. ;  rose  leaves,  ^ij.;  on-is  root,  5V.;  oils  of  mirbane, 
lavender,  and  rose-geranium,  each  gtt.  x.  Comminute  by  grating, 
cutting,  or  bruising,  and  mix. 

May-  Wine  Essence. — Coumarin,  gr.  iv. ;  spirit  of  orange  (made 
with  freshly  grated  orange  peel),  water,  each  f  ^xij.  Dissolve,  mix, 
and  if  desirable  colour  with  caramel.  A  few  ounces  are  sufficient 
to  flavour  a  gallon  of  Rhine  or  Califomian  wine. 

Ethyl  Bromide  as  an  Anaesthetic.  M.  Rabuteau.  (Comptes 
Rendus,  Ixxxiii.,  1294.)  The  author  gives  some  details  of  an  in- 
vestigation of  the  physiological  properties  and  mode  of  elimin- 
ation of  bromide  of  ethyl. 

Bromide  of  ethyl  (Co  H-  Br),  or  "  hydrobromic  ether,"  is  a 
colourless  liquid,  with  an  agreeable  odour ;  it  boils  at  about  40°  C, 
has  a  density  of  1'43,  and  bums  -nnth  difficulty.  The  boiling  point 
and  density  are  therefore  intermediate  between  those  of  chloroform 
and  sulphuric  ether. 

Bromide  of  ethyl  absorbed  by  the  respiratory  passages  produces 
absolute  anaesthesia  as  rapidly,  or  even  more  rapidly,  than  chloro- 
form. This  result  has  been  established  with  frogs,  rabbits,  dogs, 
etc.  After  five  minutes',  sometimes  after  two  minutes',  inhalation, 
by  means  of  a  sponge  saturated  in  bromide  of  ethyl,  dogs  are  com- 
pletely anaesthetized.  The  animals  recover  more  rapidly  than  when 
chloroform  is  used. 

When  a  solution  of  hydrochlorate  of  narceia  or  hydrochlorate  of 
morphia  was  injected  under  the  skin  of  dogs,  before  inducing 
anaesthesia,  an  action  was  observed  analogous,  but  perhaps  inferior, 
to  the  simultaneous  action  of  narceia  or  morphia  and  chloroform. 

Bromide  of  ethyl  is  not  caustic,  nor  even  irritant,  compared  to 
chloroform.  It  can  be  ingested  without  difficulty,  and  applied 
without  danger,  not  only  subcutaneously,  but  to  the  external  audi- 


NOTES   AND    FOEMULiE.  297 

torj  meatus  and  to  the  mncoiis  membrane.  In  tins  respect  it  is 
preferable  to  chloroform,  which  is  very  caustic,  and  to  sulphuric 
ether,  of  which  the  ingestion  is  nearly  impossible.  Introduced  into 
the  human  stomach  in  doses  of  1  to  2  grams,  bromide  of  ethyl  does 
not  produce  antesthesia  as  when  absorbed  in  suflBcient  quantity  by 
the  respiratory  passages.  It  soothes  pain,  and  does  not  disturb  the 
appetite. 

This  ansBsthetic  is  nearly  insoluble  in  water.  Nevertheless, 
water  shaken  with  it  acquires  a  pleasant  taste  and  odour.  Frogs, 
placed  in  water  so  saturated,  undergo  anaesthesia  in  ten  or  fifteen 
minutes. 

Bromide  of  ethyl  is  eliminated  nearly  entirely,  if  not  completely, 
by  the  respiratory  passages,  whatever  may  have  been  the  mode  of 
absorption.  At  most,  only  traces  of  it  are  found  in  the  urine  when 
it  has  been  introduced  into  the  stomach,  and  an  extremely  small 
quantity  can  be  detected  in  that  liquid  when  it  has  been  inhaled. 
The  author  finds  that  bromide  of  ethyl  does  not  decompose  in  the 
organism  to  form  an  alkaline  bromide,  such  as  bromide  of  sodium, 
a  salt  that  is  easily  eliminated  by  the  renal  passages. 

From  his  experiments,  the  author  concludes  that  bromide  of  ethyl 
is  an  anaesthetic  agent  possessing  properties  intermediate  between 
those  of  chloroform,  bromoform,  and  ether. 

Detection  of  Common  Resin  as  an  Adulterant  in  Shellac.  F. 
Dietlen.  {Dingl.  pohjf.  Jourii.,  ccxxii.,  190.)  Shellac  adulterated 
with  common  resin  breaks  with  a  shining  instead  of  a  dull  fracture. 

Ligroin  dissolves  common  resin  but  not  shellac,  and  may  there- 
fore be  applied  both  for  the  detection  and  the  quantitative  estimation 
of  the  adulterant. 

Hydrobromic  Acid.  Dr.  J.  Milner  Fothergill.  (British 
Med.  Journ.,  July  8,  1876.)  The  formula  for  the  production  of 
the  acid  in  quantities  of  two  quarts,  is  as  follows : — Dissolve 
3X.  5vj.  gr.  xxviij.  of  bromide  of  potassium  in  four  pints  of  water  ; 
then  add  3xiij.  5j.  gr.  xxxvij.  of  tartaric  acid.  The  bitartrate  of 
potash  is  precipitated,  and  the  hydrobromic  acid  remains  in  a  clear, 
bright,  almost  colourless  fluid,  possessing  an  acid  taste,  and  the 
ordinary  acid  properties,  as  well  as  the  peculiar  properties  of 
bromide  of  potassium  as  compared  with  any  other  salt  of  potash. 

It  prevents  the  occurrence  of  headache  after  doses  of  quinine, 
in  those  who  before  had  to  desist  from  taking  quinine  for  that 
reason.  It  is,  perhaps,  not  invariably  successful,  but  its  power  is 
very  marked.  It  also  prevents  the  fulness  felt  in  the  head  by  some 
persons,  especially  those  labouring   under  cerebral  anaemia   after 


298  YEAR-BOOK    OP    PHARMACY. 

doses  of  iron.  It  is  also  useful  after  nervous  conditions,  and,  witli 
quinine,  is  excellent  in  those  cases  when  there  is  much  nervous 
exhaustion  from  excessive  indulgence  in  tea  or  in  alcohol ;  this 
having  been  tried  in  a  case  of  nervous  excitability  and  sleeplessness 
where  there  had  been  much  resort  to  chloral  hydrate. 

In  forms  of  excited  action  of  the  heart,  connected  with  general 
nervous  excitability  or  nervous  exhaustion,  hydrobromic  acid  is 
most  useful ;  given  vnth  quinine  (of  which  it  is  a  capital  solvent) 
and  digitalis,  it  gives  better  results  than  bromide  of  potas&ium  and 
digitalis. 

In  all  hysterical  conditions  connected  with  ovarian  excitement, 
it  seems  to  have  all  the  properties  of  bromide  of  potassium.  It  is 
equally  useful  in  the  vomiting  of  pregnancy,  and  seems  to  exercise 
quite  as  powerful  an  influence  over  acts  of  reflex  origin  as  does  the 
bromide.  It  is  especially  adapted  for  the  relief  of  menorrhagia 
associated  with  sexual  excitement,  and  is  even  more  eSective  here 
than  the  bromides  themselves.  It  is  also  of  use  in  whooping-cough, 
and  combines  conveniently  with  quinine,  forming  an  effective 
measure  in  this  troublesome  aftection ;  with  spirit  of  chloroform 
and  syrup  of  squill,  it  forms  a  most  agreeable  cough  mixture  of 
no  mean  potency.  It  is  also  of  use  in  case  of  cough  of  reflex 
origin.  When  there  is  gastric  irritability,  it  is  the  most  useful  of 
all  acids,  possessing  the  usual  properties  of  acids  generally,  and  of 
the  bromine  as  well. 

The  dose  of  the  acid,  prepared  as  above,  is  one  dram  as  a  full 
dose ;  half  a  dram  is  the  quantity  ordinarily  employed.  Hydro- 
bromic acid  has  the  further  advantage  of  not  producing  the 
troublesome  eruption  so  often  the  result  of  doses  of  the  bromide 
of  potassium ;  at  least  so  far  as  the  author's  experience  has  yet 
extended.  There  are  many  qualities  about  this  acid  to  render  it 
a  useful  member  of  our  therapeutical  armamentarium.  Dr.  Wade 
states  that  it  is  useful  in  the  treatment  of  fever.  It  would  seem 
the  acid  par  excellence  Avhen  there  is  much  cerebral  excitement  in 
pyretic  affections ;  but  of  this  the  author  has  no  personal  experi- 
ence. 

The  Use  of  Salicylic  Acid  in  the  Household.     Dr.  von  Hey  den. 

1.  Raw  Meat.  —  It  frecpently  hapjiens,  especially  in  warm 
weather,  that  meat,  particularly  such  as  contains  easily  decom- 
posable fat  and  blood  (tongues,  etc.),  although  otherwise  irre- 
proachable, upon  closer  examination  or  upon  boiling,  gives  off 
a  disagreeable  smell.  This  may  easily  be  removed,  either  by 
laying  the   meat,   before  cooking,  in  lukewarm  water,  containing 


NOTES   AND    FORMULi].  299 

I  to  1  gram  of  salicylic  acid  to  the  liti-e,  or  by  throwing  some 
small  crystals  of  acid  into  the  water  during  the  boiling. 

When  it  is  desired  to  preserve  meat  for  some  days,  it  is  re- 
commended to  lay  it  in  a  solution  of  salicylic  acid  in  water,  ^ 
to  1  gram  to  the  litre ;  or  to  rnb  lightly  salicylic  acid  into  the 
meat,  especially  the  bones  and  fat  parts.  The  preservation,  as 
well  as  the  cleaning  for  the  dressing,  is  done  in  the  usual  way. 

Although  meat  treated  with  salicylic  acid  loses  its  red  colour 
on  the  exterior,  it  undergoes  no  change  internally.  Moreover, 
it  becomes  tender  with  less  boiling. 

2.  Milli. — Pure  cows'  milk,  to  which  dry  salicylic  acid  (not 
in  aqueous  solution)  has  been  added,  in  the  proportion  of  ^  to 
1  gram  to  the  litre,  curdles  at  the  ordinary  temperature  after 
about  thirty- six  hours,  retaining  its  properties,  the  cream  sepa- 
rating and  yielding  butter  perfectly. 

3.  Preserved  Fruits  (cherries,  currants,  I'aspberries,  plums,  apri- 
cots, peaches)  may  be  prepared  advantageously,  by  placing  layers 
of  fruit  and  sugar  alternately,  without  water,  in  a  not  very 
wide  mouthed  pickle  bottle,  strewing  over  them  a  pinch  of 
crystallized  salicylic  acid  (about  |  gram  to  a  kilo,  of  contents), 
closing  the  jar  with  parchment  paper  that  has  been  steeped  in 
solution  of  saKcylic  acid,  and  boiling  the  bottles  in  the  ordinary 
way  in  a  water  bath.  Bilberries  are  best  boiled  without  sugar, 
allowed  to  cool,  filled  into  a  naiTow  mouthed  flask,  some  crystal- 
lized salicylic  acid  strewn  over,  corked,  etc.  Fruit  thus  preserved 
has  been  kept  in  excellent  condition  during  two  seasons.  Another 
method  is  to  lay  over  the  surface  of  fruit  preserved  in  bottles, 
a  closely-fitting  piece  of  blotting  paper,  that  has  been  steeped 
in  a  strong  solution  of  salicyKc  acid  in  rum.  Preserved  gherkins 
may  be  similarly  treated.  For  those  preserved  in  vinegar  and 
sugar  (Essiggurken),  the  salicylic  acid  is  boiled  with  the  vinegar, 
and  when  boiled  poured  over  the  gherkins.  For  salt  gherkins 
(Snuergurl-en)  the  acid,  |  to  1  gram  to  the  litre,  is  added  during 
the  boiling ;  in  other  respects  the  preparation  is  as  usual. 

4.  Butter,  kneaded  with  water  containing  |  to  1  gram  of  salicylic 
acid  to  the  litre,  or  packed  in  cloths  saturated  in  such  a  solution, 
remains  good  longer  than  usual.  Butter  that  has  already  become 
rancid,  can  be  improved  by  careful  washing  with  aqueous  solution 
of  salicylic  acid  (2  to  3  grams  to  the  litre),  and  afterwards  rinsing 
with  pure  water. 

5.  Preserved  Vegetables,  and  similar  articles,  may  also  have  a  small 
quantity  of  crystallized  salicylic  acid  added. 


300  YKAR-BOOK    OF    PHARMACY. 

6.  Fttmlgaiion. — Diy  salicylic  acid,  volatilized  from  a  hot  plate, 
puriBes  the  air  and  perfectly  disinfects  the  walls  of  a  closed 
room. 

7.  Vessels,  GorJcs,  etc.,  to  which  a  disagi^ceable  smell  or  taste 
attaches,  are  thoroughly  purified  by  Avashing  in  solution  of  salicylic 
acid. 

The  solutions  of  salicylic  acid  for  the  above  purpose  are  best 
prepared  by  rapidly  boiling  the  acid  in  water,  in  the  proportion 
of  from  1  to  3  grams  to  the  litre,  and  leaving  to  cool.  Any  excess 
that  then  separates  is  fit  for  fresh  use ;  or  if  stirred  up  and  used  in 
suspension,  causes  a  corresponding  increase  in  the  action  of  the 
solution. 

Solubility  of  Silk  in  Alkaline  Copper  Solutions.  J.  Lowe. 
{Biiigl.  polijt.  Journ.,  187G,  274.)  Chloride  of  zinc,  hydrochloric 
acid,  and  ammoniacal  solutions  of  the  hydrates  of  nickel  and  copper 
have  been  recommended  as  solvents  for  silk.  The  author  prefers  a 
solvent  prepared  by  dissolving  16  grams  of  sulphate  of  copper  in  150 
grams  of  distilled  water,  and  adding  10  grams  of  glj-ceriu  and  so 
much  solution  of  caustic  soda  that  the  precipitate  at  first  formed  is 
just  redissolved.  This  solution,  if  made  from  pure  materials  and 
kept  in  a  stoppered  bottle,  will  remain  free  from  the  slightest  de- 
composition for  au  indefinite  period.  Silk  introduced  into  this 
solution  soon  swells  up  and  then  gradually  disappears,  forming  a 
thick,  mucilaginous  solution,  from  which  hydrochloric  acid  precipi- 
tates the  silk  as  a  whitish  jelly.  Coloured  silk  is  generally  as 
soluble  in  this  liquid  as  the  uncoloured ;  but  silk  dyed  black  with 
iron  salts  resists  the  solvent  unless  it  be  previously  immersed  in 
ammonium  sulphide,  washed  with  water,  and  treated  with  dilute 
hydrochloric  acid  to  remove  the  iron. 

Wool,  cotton,  and  linen  are  not  attacked  by  this  solvent,  not 
even  after  several  hours'  contact,  and  may  therefore  be  detected  and 
roughly  estimated  in  mixed  fabrics  containing  one  or  the  other  of 
these  materials  together  with  silk. 

Formulae  and  Preparations  of  New  Medicaments.  J.  M.  Maisch. 
(^Amer.  Jotirn.  Phann.,  1877,  2:^3.)  The  recent  French  journals 
contain  a  number  of  formulas  which  have  been  discussed  before 
the  Pharmaceutical  Society  of  Paris,  and  from  which  the  fol- 
loAving  are  selections  :  — 

THYiiic  Acid. — Add  solution  of  potassa  or  soda  to  oil  of  thyme, 
agitate  well  for  some  time,  separate  from  the  uncombined  hydro- 
carbon, decompose  the  alkaline  solution  by  hydrochloric  acid,  wash 
the  oily  liquid  with  water,  and  purify  by  distillation.     ThjTnic  acid, 


NOTES    AND    FORMDLJ;.  301 

or  flnjmol,  tlius  prepared,  is  liquid,  of  a  weaker  odour  of  thyme, 
little  soluble  in  water,  freely  soluble  in  alcohol,  possesses  caustic 
properties,  and  has  the  composition  C^q  H^j  0. 

Solution  of  Thymic  Acid  (1  per  mille) . — Dissolve  1  gram  of  thymic 
acid  in  4  grams  of  stronger  alcohol,  and  add  995  grams  of  water. 
This  solution  is  employed  in  lotions,  injections,  inhalations,  etc. 

Crystallized  Aconita. — Powdered  aconite  root  is  exhausted  by 
strong  alchohol,  containing  one  per  cent,  of  tartaric  acid ;  the  liquid 
is  distilled  at  a  moderate  heat,  contact  with  the  air  being  avoided ; 
the  residue  is  taken  up  with  water  to  remove  fatty  and  resinous 
substances,  and  then  agitated  with  ether  to  remove  colouring 
matter.  An  alkaline  bicarbonate  is  now  added  to  the  acid  aqueous 
solution  until  effervescence  ceases,  after  which  it  is  agitated  with 
ether,  the  ethereal  liquid  concentrated  and  mixed  with  some  light 
petroleum  benzin,  when  the  aconitia  will  be  obtained  in  colourless 
rhombic  or  hexagonal  tables,  which  are  soluble  in  alcohol,  ether, 
benzol,  and  chloroform,  and  insoluble  in  glycerin  and  the  oils  of 
petroleum.     Its  composition  is  represented  by  Cg^  H^q  N  Oiq- 

Crystallized  nitrate  of  aconitia  is  readily  obtained  by  neutralizing 
nitric  acid,  sp.  gr.  1"42,  with  the  alkaloid,  and  concentrating  the 
solution  ;  the  crystals  are  voluminous. 

Apomorphia. — 1  part  of  pure  morphia  and  20  parts  of  pure 
hydrochloric  acid  are  introduced  into  a  strong  tubular  glass  vessel, 
having  at  least  fifteen  times  the  capacity  of  the  mixture ;  the  open 
end  is  then  carefully  sealed,  the  tube  introduced  into  a  metallic 
tube,  closed  by  a  screw  tap,  and  the  whole  immersed  for  three 
hours  in  an  oil  bath,  heated  to  between  140°  and  160°  C.  (near 
300°  F.).  After  cooling,  the  tube  is  opened  (no  gas  being  disen- 
gaged), the  liquid  diluted  with  water,  and  bicarbonate  of  sodium 
added  in  excess,  whereby  apomorphia  mixed  with  morphia  is  pre- 
cipitated. The  liquid  is  decanted,  and  the  precipitate  exhausted  by 
ether  (or  chloroform  ?  ),  which  dissolves  only  the  apomorphia.  The 
ethereal  solution  is  mixed  with  a  few  drops  of  hydrochloric  acid,  to 
precipitate  crystalline  chlorhydrate  of  apomorphia;  the  crystals  are 
rapidly  washed  with  some  cold  water,  and  recrystallized  fi'om 
boiling  water.  To  obtain  the  new  alkaloid  from  this  hydrochlorate, 
its  concentrated  aqueous  solution  is  precipitated  by  bicarbonate  of 
sodium,  the  white  precipitate  is  rapidly  w^ashed  with  a  little  cold 
water,  and  at  once  dried. 

Thus  prepared,  apomorphia  is  a  greyish  amorphous  powder, 
which  is  pretty  freely  soluble  in  water,  the  solution  rapidly  turning 
gi'een  in  contact  with  air ;  its  solution  in  syrup,  kept  in  well-closed 


302  YEAR-BOOK    OF    PHARMACY. 

vials,  does  not  tinclergo  this  change.  It  is  distinguished  from  mor- 
phia by  its  complete  solubility  in  ether  and  benzol ;  it  is  reddened 
by  nitric  acid,  and  turns  browu  with  iodic  acid,  but  ferric  chloride 
imparts  a  rose  (not  a  blue)  colour.     Composition  C^^  H^^  N  O.j. 

Monobromated  camphor  is  recommended  to  be  prepared  by  pouring 
upon  camphor  contained  in  a  retort  a  thin  stream  of  bromine  until 
the  camphor  is  liquefied,  heating  by  a  water  bath  until  bromhydric 
acid  ceases  to  be  given  off,  and  crystallizing  tlie  residue  from  boiling 
alcohol. 

Cataplasm  of  Fdcus  Crispos. — A  sheet  of  carded  wadding  is 
evenly  spread  out,  a  concentrated  mucilaginous  infusion  of  Fucus 
crispus  (Irish  moss)  poured  on  it,  and  this  covered  with  another 
sheet  of  wadding  of  tlie  same  size.  By  beating  lightly  with  a  brush 
the  jelly  is  made  to  penetrate  the  wadding  veiy  evenly,  and  the 
whole  is  exposed  to  the  moderate  heat  of  a  drying  closet  until  the 
water  has  been  expelled,  when  it  resembles  a  sheet  of  thick  cotton, 
and  has  acquired  no  odour.  When  intended  for  use,  sufficient  of 
the  wadding  is  placed  in  a  large  plate  and  moistened  with  nearly 
boiling  water,  whereby  the  jelly  swells  considerably,  the  saturated 
solution  of  the  emollient  principles  of  the  fucus  remaining  inclosed 
in  the  wadding. 

Strupof  Chlorhtdrophosphate  op  Calcium. — 12'50  grams  calcium 
phosphate  (prepared  by  precipitating  chloride  of  calcium  with  phos- 
phate of  sodium)  are  diffused  in  34-0  gTams  distilled  water,  and  just 
sufficient  (about  8  gi'ams)  hydrochloric  acid  added  to  dissolve  the 
calcium  salt ;  630  grams  white  sugar  are  dissolved  in  the  liquid 
without  heat,  and  10  grams  essence  of  lemon  mixed  with  the 
strained  syrup.  Syrap  of  lactophosphate  of  calcium  is  prepared 
like  the  preceding  fi'om  12'50  gi'ams  calcium  phosphate,  sufficient 
(about  14  grams)  concentrated  lactic  acid,  340  gi'ams  distiUed 
water,  630  grams  sugar,  and  10  grams  essence  of  lemon. 

Syrup  of  acid  phosphate  of  calcium  is  prepared  in  precisely  the 
same  manner,  only  substituting  for  the  lactic  acid  a  just  sufficient 
quantity  (about  18  grams)  of  phosphoric  acid,  sp.  gi\  1'45. 

The  solutions  corresponding  to  the  three  syrups  above  are  made 
by  employing  17  grams  of  the  calcium  phosphate,  increasing  the 
corresponding  acid  in  proportion,  and  using  enough  distilled  water 
to  make  the  whole  weigh  1000  grams. 

Glycerite  of  Sucrate  of  Calcium. — Mix  80  grams  of  burnt  lime 
with  160  of  sugar,  and  add  in  small  quantities  gradually  100  grams 
of  water.  After  twenty-four  hours,  filter  ;  add  to  the  filtrate  160 
grams  glycerin,  and  enough  water  to  make  1  litre. 


NOTES    AXD    FORMULAE.  303 

Liniment  of  Sucbate  of  Calcium. — Olive  oil,  200  grams;  glycerite 
of  sucratc  of  calcium,  100  gi-ams.     Mix. 

Infusion  of  Coca. — Coca  leaves,  10  gi-ams ;  boiling  water,  1000 
grams. 

Wine  of  Coca. — Bruised  coca  leaves,  30  grams ;  60  per  cent, 
alcohol,  60  grams.  Macerate  for  twentj-four  hours,  then  add  wine 
(vin  de  Lunel),  1000  grams.  Macerate  for  ten  days  with  frequent 
agitation,  and  filter. 

Elixir  of  Coca. — Coca  leaves,  100  grams ;  60  per  cent,  alcohol, 
600  grams.  Macerate  for  ten  days  ;  express  strongly,  and  mix  the 
liquid  with  400  grams  simple  syrup  ;  filter. 

Extract  of  Coca  is  made  by  displacement  Math  60  per  cent,  alco- 
hol, and  evaporation  to  a  soft  extract. 

Syrup  of  Coca. — Coca  leaves,  100  grams  ;  boiling  water,  1000 
grams.  Infuse  for  twenty-four  hours,  express,  filter,  and  dissolve 
175  grams  sugar  in  each  100  grams  of  the  filtrate. 

loDiNiZED  Cotton. — 2  grams  of  finely  powdered  iodine  are  sprinkled 
over  25  grams  of  cotton  as  uniformly  as  possible,  which  is  then 
introduced  into  a  wide  mouthed,  glass  stoppered  bottle  that  has 
been  kept  for  a  few  minutes  in  nearly  boiling  water  to  expel  some 
air.  The  stopper  is  then  securely  fastened,  and  the  bottle  heated 
for  at  least  two  hours  to  a  temperature  of  100°  C,  until  the  cotton 
has  become  uniformly  impregnated  with  the  iodine.  The  bottle 
must  be  allowed  to  cool  before  it  is  opened;  and  the  cotton,  which 
contains  8  per  cent,  of  iodine,  must  be  kept  in  glass  stoppered  vials. 
(See  also  Year-Boole  of  Phannacy,  1876.) 

Diastase. — Malt,  of  which  the  germ  has  attained  two-thirds  the 
length  of  the  barley  grain,  and  dried  at  50°  C,  is  ground,  macerated 
at  the  ordinary  temperature  for  five  or  six  hours  with  twice  its  weight 
of  water ;  then  expressed,  filtered,  and  the  liqiiid  mixed  with  twice 
its  bulk  of  95  per  cent,  of  alcohol.  The  precipitate  is  collected, 
spread  in  thin  layers  upon  plates  of  glass,  and  rapidly  dried  in  a 
current  of  air  at  a  temperature  of  45°  C. 

85  grams  of  diastase  added  to  200  grams  of  paste  containing  10 
grams  of  starch  yield  a  liquid  which  filters  very  readily,  and  deco- 
lorizes five  times  its  volume  of  Fehling's  solution. 

Syrup  of  Chloral  Hydrate. — Dissolve  50  grams  of  crystaUized 
chloral  hydi'^te  in  950  gi^ams  of  orange-flower  syrup.  A  table- 
spoonful  (20  gi'ams)  contains  1  gram  of  chloral  hydrate. 

Tincture  of  Quillaia. — 100  grams  of  quillaia  bark  are  digested  in 
500  grams  of  alcohol  in  a  suitable  apparatus,  placed  in  a  water  bath, 
the  temperature  being  maintained  near  the  boiliag  point  for  half 


804  TEAR-BOOK    OF    PHARMACY. 

an  hour ;  the  whole  is  then  macerated  for  48  houi's  -with  occasional 
agitation,  and  afterwards  filtered.  The  tincture  is  mainly  employed 
ia  preparing  emulsions  of  substances  insoluble  in  water,  such  as  co- 
paiba,  tar,  oil  of  cade,  which  are  made  according  to  tlie  formula  for — 

Emulsion  of  Tolu  Balsam. — Dissolve  2  grams  of  balsam  of  tolu 
in  10  grams  of  90  per  cent,  alcohol,  add  10  grams  of  tincture  of 
quillaia,  and  mix  with  78  grams  of  hot  water. 

Preparations  of  Eucalyptus  Globulus. — The  infusion,  wine, 
elixir,  and  extract  are  made  from  eucalyptus  leaves,  in  the  same 
manner  as  the  corresponding  preparations  of  coca,  (see  p.  303.) 

Water  of  Eucalyptus. — Distil  1  part  of  dry  eucalyptus  leaves  with 
sufficient  water  to  obtain  4  parts  of  distillate. 

Si/rup  of  Eucalyptus. — Infuse  50  grams  of  eucalyptus  leaves  foi* 
three  hours  with  sufficient  water  to  obtain,  after  expressiou  and 
filtration,  250  grams  of  infusion;  add  100  grams  of  distilled  eucalyp- 
tus water,  and  dissolve  in  the  liquid  650  gi-ams  of  sugar,  using  a 
covered  vessel  placed  in  a  water  bath. 

Tincture  of  Physostigma. — Macerate  100  parts  of  powdered 
Calabar  bean  in  500  parts  of  80  per  cent,  alcohol  for  10  days ; 
express  and  filter. 

Glycerite  of  Extract  of  Physostigma  is  made  in  three  diflferent 
proportions.  The  alcoholic  extract  of  Calabar  bean  is  well  mixed 
with  10,  20,  or  100  times  its  weight  of  glycerin,  and  dissolved  by  the 
aid  of  a  moderate  heat.     It  sho^^ld  be  completely  dissolved. 

Bromide  of  Iron. — The  solution  of  this  salt  does  not  keep  well, 
and  is  at  once  made  up  into  syrup  or  pills.  It  is  made  by  using 
40  grams  of  iron  filings,  216  grams  distilled  water,  and  80  grams 
bromine,  and  contains  one-third  its  weight  of  ferrous  bromide. 

Pills  of  Ferrous  Bromide. — 15  grams  of  the  preceding  solution 
and  10  grams  powdered  iron  are  evaporated  in  a  porcelain  capsule, 
until  the  water  has  been  driven  oif ;  the  mass,  while  still  hot,  is 
transferred  to  a  warm  mortar,  mixed  with  sufficient  powdered  gum 
arable  and  licorice  root  until  a  mass  is  obtained,  which  is  divided 
into  100  pills  ;  they  are  to  be  rolled  in  lycopodium  or  covered  with 
a  mixture  of  gum  and  sugar. 

Syrup  of  Ferrous  Bromide. — 15  grams  of  the  solution  are  mixed 
with  985  grams  of  syrup  of  gum,  flavoured  with  orange-flower  water. 

Ferrous  Chloride  is  made  by  dissolving  iron  in  hydrochloric  acid 
and  evaporating  the  filtered  solution  rapidly  to  dryness. 

Syrup  of  Ferrous  Chloride. — Dissolve  5  grams  of  dry  ferrous  chlo- 
ride in  20  grams  of  orange-flower  water,  and  add  800  grams  syrup 
of  gum  and  175  grams  syrup  of  orange-flower. 


NOTES   AND    FOKMUL.T;.  305 

•  Pills  nf  Ferrous  Chloride. — Dry  ferrous  cliloride,  powdered  marsli- 
raallow-root,  each  10  grams,  mucilage  sufficient.  Make  into.  100 
pills,  which  are  to  be  silvered. 

DiALYSED  Oxide  of  Iron. — 100  grams  solution  of  ferric  chloride 
of  30°  B.,  are  mixed  in  small  quantities  with  o5  grams  ammonia 
water  of  22°  B.  The  precipitate  dissolves  at  first  rapidly,  afterwards 
very  slowly.  When  the  liquid  has  become  transparent  it  is  intro- 
duced into  a  dialysator,  and  this  placed  in  distilled  water,  which  is 
to  be  frequently  renewed,  until  the  liquid  is  no  longer  precipitated 
by  nitrate  of  silver  and  is  destitute  of  acid  reaction.  It  still  contains 
a  small  quantity  of  hydrochloric  acid,  which  may  be  recognised  by 
precipitating  with  ammonia,  acidulating  with  nitric  acid,  and  testing 
with  silver  nitrate.  10  c.c.  of  the  liquid,  which  is  entirely  free  from 
disagreeable  ferruginous  taste,  are  evaporated,  and  from  the  weighed 
residue  the  amount  of  water  is  calculated  which  must  be  added  to 
obtain  a  solution  containing  in  100  c.c.  1  gram  of  solid  matter. 

Syrup  of  Ferrous  Chlorhydro-phosphate. — Ferrous  chloride,, 
medicinal  phosphoric  acid,  of  each  5  grams  ;  distilled  water,  350 
grams ;  sugar,  64<0  grams.     Make  a  syrup. 

Syrdp  of  Pyrophosphate  of  Iron  and  Sodidm. — Dissolve  25 
grams  of  sodium  pyrophosphate  in  250  grams  of  distilled  water,  and 
5  grams  of  dry  ferric  sulphate  in  100  grams  of  water  ;  add  this  last 
to  the  former  solution,  and  in  the  clear  and  colourless  liquid  dissolve 
620  grams  of  sugar. 

The  solutions  of  the  last  two  preparations  are  obtained  by  omitting 
the  sugar  and  adding  enough  distilled  water  to  make  1  litre  of 
solution. 

Gi.YCERiTEs  OF  SuBNiTRATE  OF  BiSMUTH,  of  laudanum,  of  extract 
of  lead,  and  of  extract  of  i-hatany  are  made  with  1)0  parts  glycerite 
of  starch,  by  mixing  it  intimately  with  10  parts  of  subAitrate  of  bis- 
muth, of  Sydenham's  Laudanum,  of  Goulard's  Extract,  or  of  extract 
of  rhatany,  the  latter  to  be  previously  dissolved  in  the  smallest 
possible  quantity  of  glycerin 

Tar  Water. — The  wood  tar  should  be  of  a  red-brown  colour, 
transparent,  and  free  from  resinous  deposits.  Mix  5  grams  of  such 
tar  intimately  with  10  grams  of  pine- wood  sawdust,  and  macerate 
for  twenty-four  hours  with  1000  grams  of  distilled  or  rain  water, 
stirring  frequently. 

Syrup  of  Tar. — 15  grams  of  tar  and  30  grams  pine-wood  saw- 
dust are  mixed,  and  digested  at  60°  C.  with  1000  grams  water,  with 
occasional  agitation.  Filter  at  the  end  of  two  hours  upon  the  sugar, 
190   grams  of  which  are  to  be  used  for  every  100  grams  of  the  fil- 


'306  YEAR-BOOK    OF    PHARMACY. 

trate,  and  effect  the  solution  in  a  closed  vessel,  heating  it  by  means 
of  a  water  bath. 

Strcp  of  Iodotannin  (Sirop  lodotannique). — Dissolve  1  gram  of 
iodine  in  11  grams  of  90  per  cent,  alcohol,  add  to  syrup  of  rhatany 
(containing  2-5  per  cent,  of  extract  of  rhatany)  988  grams,  and  mix 
well.  The  combination  will  be  completed  at  the  ordinary  tempera- 
ture in  twenty-four  hours,  when  the  syrup  has  again  its  original 
colour. 

lODiNiZED  Strup  OF  HORSERADISH  is  made  in  precisely  the  same 
way  as  the  preceding,  substituting  the  same  weight  of  compound 
syrup  of  horseradish. 

Syrup  of  Iodide  of  Starch. — Dissolve  10  grams  of  soluble  iodide 
of  starch  in  330  grams  of  distilled  water,  and  use  this  solution  for 
dissolving  640  grams  of  sugar,  by  the  aid  of  a  gentle  heat. 

PiLOCARPiNA. — The  leaves  or  bark  of  Pilocarpus  pennatifolius  are 
exhausted  with  80  per  cent,  alcohol,  containing  in  the  litre  8  grams 
of  hydrochloric  acid,  and  the  tincture  is  distilled  and  evaporated  to 
the  consistency  of  a  liqiiid  extract,  which  is  mixed  with  a  small 
quantity  of  water,  and  filtered.  The  filtrate  is  treated  with  a  slight 
excess  of  ammonia,  and  then  with  a  large  quantity  of  chloroform. 
The  chloroform  solution  is  agitated  with  water,  to  which  hydro- 
chloric acid  is  added,  drop  by  drop,  in  sufficient  quantity  to  neutra- 
lize the  alkaloid,  the  hydrocblorate  of  which  is  obtained  in  long 
needles  on  evaporating  the  aqueous  solution,  while  foreign  principles 
remain  dissolved  in  the  chloroform.  By  dissolving  the  crystals  in 
water,  treating  the  solution  with  ammonia  and  chloroform,  and 
evaporating  the  latter  solution,  pilocarpina  is  obtained  as  a  soft 
viscous  mass,  which  is  little  soluble  in  water,  but  freely  soluble  in 
alcohol,  ether,  and  chloroform. 

Effervescing  Carbonate  of  Lithium. — Take  of  citric  acid  40 
grams,  bicarbonate  of  sodium  50  grams,  and  carbonate  of  lithium 
10  grams.  Powder  and  mix  well,  then  introduce  into  a  wide  flat- 
bottomed  dish,  and  heat  to  about  100°  C.  (212° F.),  stirring  con- 
stantly until  the  powder  becomes  granular.  Separate  the  ganules  of 
uniform  size  by  means  of  appropriate  sieves,  and  preserve  theto  in 
well-stoppered  bottles. 

Extract  of  Malt. — Take  of  malt,  the  germ  of  which  has  attained 
two-thirds  the  length  of  the  grain,  dry  at  50° C.  (122° F.),  grind  and 
treat  it  with  2  parts  of  water  at  the  ordinary  temperature,  stir- 
ring the  mixture  occasionally.  After  five  or  six  hours  express,  strain, 
filter,  and  evaporate  in  a  shallow  dish  at  a  temperature  not  exceed- 
ing 45°  C  (113°F.) 


NOTES   AND    FORMULA.  307* 

Strup  of  Narceina. — Dissolve  1  gram  of  narceiua  in  100  grams 
of  water  containing  "6  gram  hydrochloric  acid  ;  add  to  the  solution 
250  grams  of  water,  and  then  dissolve  650  grams  of  white  sugar. 
Eiach  tablespoonful  of  20  grams  contains  '02  gram  (J  gi-ain)  of 
narceina. 

Panceeatin. — Pancreas  is  freed  from  foreign  matters,  bruised  and 
mixed  with  water  containing  some  chloroform,  to  prevent  decomposi-* 
tion.  After  some  time  the  mass  is  expressed,  and  the  liquid  filtered 
and  evaporated  rapidly  in  shallow  dishes  by  means  of  a  current  of 
air,  at  a  temperature  not  exceeding  45° C.  (113°F.)  -10  gram  of 
pancreatin  disgested  with  5  grams  of  fibrin  and  25  grams  of  water, 
at  a  temperature  of  50°  C.  (122°  F.)  for  twelve  hours,  yields  a  solution 
which,  when  filtered,  is  scarcely  rendered  turbid  by  the  addition  of 
nitric  acid.  "10  gram  of  pancreatin,  added  to  100  grams  of  paste 
containing  5  grams  starch,  yield  a  liquid  which  filters  easily  and 
decolorizes  four  times  its  volume  of  Fehling's  solution. 

Ferroctanhydrate  of  Quinia. — Four  parts  of  quinia  sulphate  and 
enough  distilled  water  to  form  a  not  too  thick  mixture  are  mixed 
with  a  concentrated  solution  of  one  part  of  ferrocyanide  of  potassium; 
the  whole  is  heated  to  boiling  for  a  few  seconds,  and  then  allowed 
to  cool.  The  mother-liquor,  from  which  more  of  the  salt  is  obtained 
DU  concentration,  is  poured  oS"  from  the  resin-like  mass,  the  latter 
washed  with  hot  water  and  crystallized  from  boiling  alcohol. 
It  is  in  small  yellowish  needles,  bitter,  slightly  soluble  in  water, 
freely  in  alcohol,  and  efflorescent  in  the  air. 

Bromhtdrates  of  Quinia. — The  basic  salt  is  obtained  by  heating 
10  grams  of  quinia  sulphate  with  80  grams  of  water  to  boiling,  and 
adding  3"40  grams  dry  barium  bromide,  dissolved  in  20  grams  of 
water;  the  sulphate  of  barium  is  filtered  off  and  the  filtrate  evapo- 
rated and  crystallized.  It  forms  silky  needles,  which  require  60 
parts  of  cold  water  for  solution. 

The  neutral  salt  is  made  in  a  similar  manner,  except  that  the 
quinia  is  dissolved  by  the  aid  of  just  sufficient  sulphuric  acid,  and 
6"80  grams  of  barium  bromide,  dissolved  in  25  grams  of  water,  are 
used  for  decomposition;  the  mixture  is  heated  to  boiling,  filtered, 
the  filtrate  evaporated  to  35  grams,  and  crystallized.  It  crystallizes 
in  handsome  prisms,  which  are  soluble  in  7  parts  of  cold  water,  and 
freely  soluble  in  alcohol  and  hot  water.  Both  salts  must  be  free 
from  barium. 

Tannate  of  Quinia. — To  a  neutral  solution  of  quinia  salt  add  a 
.solution  of  gallotannic  acid,  free  from  resinous  matter,  until  the 
white  precipitate  is  redissolved  ;   neutralize  exactly  with  solution  of 


308  TEAR-BOOK    OF    PHARMACY. 

bicarbonate  of  sodium,  whereby  the  quinia  tannate  will  be  precipi- 
tated; collect  upon  a  filter,  drain,  dry, powder,  and  wash  with  distilled 
water  ;  then  dry  again.  It  is  a  white  amorphous  powder,  3"5  parts 
of  which  correspond  with  1  part  of  quinia  sulphate;  if  prepared 
from  the  latter  salt,  it  always  retains  a  certain  quantity  of  sulphuric 
acid. 

Lactate  op  Sodium  is  made  by  neutralizing  lactic  acid  with  sodium 
bicarbonate,  and  evaporating.     It  is  very  deliquescent. 

SuLPHOVlNATE  OF  SoDlCM. — 1000  grams  of  sulphuric  acid  are 
carefully,  and  with  constaut  agitation,  added  to  1000  grams  of 
strong  alcohol,  and  set  aside  for  several  hours  ;  the  liquid  is  then 
diluted  with  4  litres  of  distilled  water,  neutralized  with  barium 
carbonate,  and  filtered  from  the  precipitated  barium  sulphate.  The 
filtrate  is  decomposed  by  a  solution  of  sodium  carbonate,  and  the 
filtrate  concentrated  in  a  water  bath  and  set  aside  to  crystallize ;  if 
necessary,  the  crystals  are  purified  by  recrystallization  from  water, 
and  when  dry  preserved  in  well-stoppered  bottles.  The  yield  is  about 
1000  grams.  The  salt  forms  hexagonal  tables,  which  are  very 
soluble  in  alcohol  and  water,  have  a  scarcely  bitterish  taste,  and 
when  heated  to  120° C.  (248°F.)  liberate  alcohol.  Its  aqueous 
solution  is  not  precipitated  by  barium  chloride  or  by  potassium 
sulphate. 

Syrup  of  Hypophosphite  of  Sodium. — Dissolve  6  grams  of  the 
salt  in  445  grams  of  simple  syrup,  and  add  50  grams  of  orange- 
flower  syrup.  A  tablespoonful  weighing  20  grams  contains  0'20 
grams  (3  grains)  of  sodium  hypophosphite. 

The  Pharmaceutical  Preparations  of  Physostignia.  G.  W. 
Kennedy.  (Abstracted  from  a  paper  read  at  the  fifth  session  of 
the  American  Pharmaceutical  Association.)  The  writer  does  not 
favour  the  use  of  strong  alcoholic  preparations,  as  the  active  prin- 
ciple of  Calabar  bean  is  best  extracted  by  a  mixture  of  alcohol  and 
water.  The  follomng  embraces  all  the  preparations  of  the  bean 
which  have  hitherto  been  in  use  : — 

JExtradum  PJujsostigmatis. 

Ps     Calabar    Bean    in   moderately  fine 

powder  .....  12  troy  ounces. 

Alcohol  (95  per  cent.)      ...  9  fluid      ,, 

Water  (distilled)       .         .         .         .  3     „ 

Glycerin 1     ,,         ,, 

Mix  the  alcohol,  water,  and  glycerin  together;  moisten  the  pow- 
der with  five  fluid  ounces  of  the  mixture,   pack  in  a  conical   glass 


NOTES    AND    FORMULA.  309 

pBVuolator,  and  cover  the  surface  of  the  powder  with  a  disc  of 
paper ;  pour  on  the  bahxnce  of  the  mixture,  cork  the  percolator, 
and  cover  closely,  and  set  aside  in  a  moderately  warm  place  for  four 
days,  after  which  remove  the  cork,  and  proceed  with  the  percola- 
tion, with  a  menstruum  composed  of  three  parts  alcohol  and  one 
part  water,  until  completely  exhausted ;  distil  oiF  the  alcohol,  and 
evaporate  in  a  porcelain  vessel  by  means  of  a  water  bath  to  the 
proper  consistence.  The  object  of  the  glycerin  is  to  keep  the  ex- 
tract in  a  soft  condition,  which  makes  it  more  convenient  for  mani- 
[)ulation,  and  especially  when  it  forms  one  of  the  component  parts 
of  a  pill  mass. 

Extradum  Physostigmatis  Fhddum. 

5b     Calabar  Bean    in    moderately    fine 

powder  ......  16  troy  ounces. 

Alcohol  (95  per  cent.)        .         .         .  12  flnid      ,. 
Water  (distilled)       .         ,         .         •       i     „ 

Moisten  the  powder  with  six  fluid  ounces  of  the  above  men- 
struum ;  pack  in  a  conical  glass  percolator,  after  which  cover  the 
surface  of  the  powder  with  a  disc  of  paper,  and  pour  upon  it  a  suf- 
ficient quantity  of  the  menstruum  until  the  liquid  begins  to  drop 
from  the  percolator ;  then  close  the  lower  aperture  with  a  cork, 
and  cover  closely,  and  set  aside  in  a  moderately  warm  place  for  four 
days,  after  which  the  cork  should  be  removed,  and  more  men- 
struum added  until  thoroughly  exhausted,  the  first  twelve  ounces 
being  reserved,  and  the  balance  to  be  evaporated  to  four  fluid 
ounces,  and  mixed  with  the  reserved  portion,  and  after  standing  a 
few  days  should  be  filtered  through  jjaper.  This  prejiaration  is  but 
little  used,  but  makes  an  excellent  basis  for  preparing  calabarized 
paper  or  calabarized  gelatin. 

Tinctura  Physostigmatis. 

^     Calabar    Bean    iu    moderately    fine 

powder 4  troy  ounces. 

Alcohol  (95  per  cent.)        .         .         .  24  fluid      ,, 

"Water  (distilled)       .         .         .         .  8     „ 

Mix  the  alcohol  and  water ;  moisten  the  powder  with  two  fluid 
ounces  of  the  menstruum  ;  pack  in  a  conical  glass  percolator,  and 
<;over  the  surface  of  the  powder  with  a  disc  of  paper,  and  pour  six 
fluid  ounces  of  the  above  menstruum  on  it ;  cork  and  cover  the 
{lercolator  closely,   and  allow  it  to  remain  in  this   condition  foui 


310  YEAR-BOOK    OF    PHARMACr. 

days,  after  which  remove  the  cork,  and  proceed  with  the  percola- 
tion and  with  the  same  menstruum  until  two  pints  of  tincture  are 
obtained,  which  will  be  found  sufficient  to  thoroughly  exhaust  the 
bean.  Some  of  the  formulae  which  have  been  published  for  makinir 
this  preparation  contain  a  much  larger  proportion  of  the  bean. 
The  writer's  object  in  mating  it  four  troy  ounces  to  the  quart  of 
tincture  is  to  make  it  conform,  in  the  proportion  of  solid  material, 
with  most  other  tinctures. 

Cnlabarized  Paper. 

This  is  readily  prepared  by  taking  paper  deprived  of  its  size — 
thin  letter  paper,  not  ruled,  is  the  best — and  the  size  got  rid  of  by 
boiling  in  water  and  drying.  By  dipping  the  paper  three  or  four 
times  in  the  fluid  extract,  and  drying  it  after  each  immersion,  the 
paper  will  be  impregnated  with  a  sufficient  amount  of  the  extract 
to  perform  the  necessary  service  when  applied  to  the  eye.  This 
plan  of  obtaining  the  effijcts  of  Calabar  bean  is  objectionable,  by 
being  inconvenient,  as  it  necessitates  the  removal  of  the  paper  sub- 
sequently. Calabarized  gelatin  is  a  much  preferable  preparation, 
for  which  the  following  formula  is  recommended : — 

Calabarized  Gelatin. 

$b     Gelatm 30  grains. 

Water  (distilled)       ....     2  fluid  ounces. 

Glycerin  .......         gtt.  xx. 

Fluid  Extract  Physostigma      .         .         .         .     rry.  c. 

Make  a  solution  of  the  gelatin  in  the  w%ater  and  glycerin,  and, 
while  the  solution  is  still  warm,  filter  through  paper  in  a  warm 
funnel ;  add  the  fluid  extract,  and  evaporate.  When  it  is  evapo- 
rated to  the  proper  consistence,  spread  on  a  glass  plate  or  marble 
slab,  with  edges  slightly  raised,  and  with  perfectly  even  surface, 
and  place  another  glass  plate  or  slab  on  top,  which  will  keep  it 
even  and  smooth  ;  when  it  is  hard  enough,  remove  the  plates,  and 
divide  into  one  hundred  equal  squares  of  about  an  eighth  of  an  inch, 
square,  or,  as  some  might  perhaps  prefer,  in  circular  form.  The 
object  here  of  the  glycerin  is  to  prevent  its  brittleness.  The  slabs 
.should  be  slightly  greased  and  warm,  so  as  to  prevent  the  shrink- 
ing and  sticking  of  the  gelatin.  One  of  these  small'discs,  containing 
about  one  grain  of  the  bean,  placed  in  the  eye,  will  be  immediately 
dissolved  by  the  secretions,  and  the  remedial  agent  absoi'bed,  and 
the  effijcts  of  the  bean  produced. 


NOTES   AND    FORMDL.E.  311 

Physostigmine 

is  obtained  by  treating  the  extract  as  prepared  according  to  the 
formula  given,  with  a  small  quantity  of  dilute  sulphunc  acid,  and 
diluting  the  mixture  with  water,  filtering,  and  supersaturating  with 
ammonium  carbonate.  The  whole  is  now  shaken  with  strong  ether, 
and  the  ethereal  solution  which  contains  the  alkaloid  is  separated 
after  standing,  which  yields  on  evaporation  the  physostigmine  in  an 
impure  condition,  being  contaminated  with  a  red  foreign  matter, 
which  obstinately  adheres  to  it,  and  requires  repeated  solution  in 
ether  and  crystallization  to  remove  all  the  impurities. 

The  Syrups  of  Phosphates  in  General  Use.  E.  C.  Saunders. 
(Pharm.  Jouni.,  ord  series,  vii.,  41.)  The  chief  reason  for  the  dif- 
ference met  with  in  the  various  makes  of  the  preparation  known  as 
"  Parrish's  Chemical  Food  "  is  to  be  found  in  the  fact  that  the  prin- 
cipal published  formula,  that  in  Parrish's  "  Pharmacy,"  is  an  utterly 
unpractical  one.  It  is  well  known  that  glacial  phosphoric  acid  un- 
contaminated  with  phosphate  of  soda  is  hardly  to  be  found  in  the 
market  at  present ;  but  even  if  it  were,  it  is  next  to  impossible  to 
obtain  a  good  preparation  with  it,  as  it  is  a  monobasic  acid,  while 
the  direction  to  add  "  quantum  S7ifficit  "  of  hydrochloric  acid  is  ex- 
ceedingly vague.  But  apart  from  this,  it  is  evident  that  the  for- 
mula cannot  be  strictly  followed,  as  if  the  quantity  of  ferrous  phos- 
phate directed  to  be  present  in  each  fluid  dram  of  the  completed 
syrup  is  attended  to,  thirty-two  troy  ounces  of  sugar  will  have  to 
be  made  into  thirty-six  fluid  ounces  of  syrup, — a  manifest  impossi- 
bility ;  while  if  the  quantity  given  as  the  amount  of  solution  to  be 
formed  for  the  sugar  to  be  dissolved  in  is  adhered  to,  the  result  will 
be  about  forty-six  fluid  ounces  of  syrup,  which  will  not  contain  the 
requisite  amount  per  dram  of  iron  and  lime.  All  the  formulae  at 
present  in  use  seem  merely  modifications  of  that  given  by  Parrish. 
In  the  following  formula,  the  author  has  only  followed  Parrish  as 
far  as  the  result  to  be  obtained  is  concerned,  viz.,  that  the  finished 
syrup  shall  contain  in  each  fluid  dram  one  grain  ferrous  phos- 
phate Fe.5  Po  Og,  2|  grains  calcic  phosphate  Ca.5  Po  Og,  and  traces  of 
sodic  and  potassic  phosphates,  with  free  phosphoric  acid. 

p,  Iron  Wire  (clean,  No  20)  .  .  .  2-iO  grains. 
Syrupy  Phosphoric  Acid  (sp.gr.  1'75),  3  oz.  by  weight. 
Water  (distilled)     ....       4  fluid  ounces. 

Mix  the  acid  and  water,  and  dissolve  the  wire  in  the  mixture  in 
a  flask,  loosely  stopped  with  tow;  the  hydrogen  evolved  then  pi-o- 
tects    the   solution  from  oxidation.     When  all  action  has  ceased. 


812 


YEAK-BOOK    OF    PHARMACY. 


heat  to  boiling  })oint,  and  filter  tlirouo-h  pa})er  in  a  funnel  with  a 
long  neck  reaching  tp  the  bottom  of  a  beaker  containing  a  little 
syrup,  -vvliicli  floating  on  the  iron  solution  will  effectually  prevent 
any  oxidation. 

|l     Slaked  Lime  (fresh)        ....     923  grains. 

Phosphoric  Acid  (sp.  gr.  1-75)         .  9J  oz.  by  weight. 

Water  (distilled)     .         .         .         .14  fluid  ounces. 

Mix  the  acid  and  water,  and  di.ssolve  the  lime  in  the  mixture. 
Filter  the  solution. 

5c     Crystallized  Sodic  Carbonate  .        ,        .54  grains. 

Potassic  Carbonate 72  gi-ains. 

Phosphoric  Acid  (sp.  gr.  1-75)  .         •  |  oz.  by  weight. 
Water  (distilled)       ....       1  fluid  ounce. 

Dissolve  and  filter.  Then  mix  all  the  solutions  ;  and  having  added 
distilled  water  to  make  the  solution  measure  28  fluid  ounces,  dis- 
solve in  it,  with  heat,  sugar,  3j ;  powdered  cochineal,  85  grains; 
and  strain  wliile  bot.  When  cold  add  orange-flower  water,  2  fluid 
ounces,  and  sufficient  distilled  water  to  make  the  wbole  measure 
64  fluid  ounces.  The  product  is  a  nice  clear  syrup,  entirely  free 
from  sulphate  of  soda,  or  amnionic  chloride,  both  of  which  are  b}' 
no  means  uncommon  impurities- -from  the  difficulty  of  washing  thci 
precipitates — when  the  syrup  is  made  in  the  old  way  ;  while  thei 
whole  process  will  be  found  very  much  less  troublesome  and  tedious. 
Calcic  hydrate  is  generally  sufficiently  pui-e  as  commonly  obtained  ; 
though  where  the  chemist  has  the  facilities  for  doing  it,  it  is  besii 
for  him  to  make  the  lime  himself,  by  igniting  precipitated  chalk  in 
a  crucible  at  a  full  red  heat  for  an  hour. 

It  may  be  remarked  here  that  the  last  edition  (1872)  of  Pereira's 
"  Materia  Medica  "  contains  the  astonishing  information,  on  page 
213,  that  "  Hypophosphite  of  lime  is  an  important  constituent  in 
Parrislrs  chemical  food  " — a  statement  that  is  liable  to  mislead 
physicians  in  a  serious  manner. 

Eas ton's  syrup  is  another  preparation  that  is  frequently  badly 
made,  and  very  often  deficient  in  iron.  The  precipitate  so  fre- 
•  piently  met  with,  in  the  form  of  phosphate  of  quinine,  is  probably 
always  owing  to  the  use  of  an  acid  containing  metaphosphoric  acid. 
The  change  in  colour  is  due  to  exposure  to  the  air,  chiefly  from 
oxidation  of  the  iron  salt,  but  partly  to  the  quinine  changing  colour. 
It  may  be  entirely  avoided,  as  has  been  often  remarked,  by  com- 
pletely filling  the  bottles  in  which  the  syrup  is  kept,  and  corking  so 
as  to  have  as  little  air  left  in  the  bottle  as  possible. 

No   trouble  will  be  found  in 'making  a   satisfaclury  preparation 


NOTES  AND  rouMUL.?^:.  313 

if  the  following  formula   be  strictly  followecl,   and  care  taken  to 
avoid  exposure  to  the  air  of  the  iron  solution. 

R     Ii-on  Wire  (No.  20)         ...         .     240  grains. 
Phosphoric  Acid  (sp.  gr.  1-7'j)  .     3  oz.  by  weight. 

Water     ......        4  fluid  ouuces. 

Dissolve,  with  the  precautions  directed  above  in  the  formula  for 
Parrish's  syrup. 

Pi    Quinine  Sulph 625  grains. 

Liq.  Arumon., 

Distilled  Water, 

Dilute  Sulphuric  Acid    .         .         .         .         .  aa  q.  s. 

Precipitate  the  quinine,  secundum  artcm,  and  wash  on  a  filter  with 
a  pint  of  very  cold  distilled  water,  press  strongly,  and  dissolve  in 
half  an  ounce  by  weight  of  phosphoric  acid,  diluted  with  an  ounce 
of  water  in  which  sixteen  grains  of  strychnine  have  been  dissolved. 
Mix  with  the  solution  of  iron,  add  enough  distilled  water  to  make 
the  whole  measure  10  fluid  ounces,  and  mix  thoroughly  with  54 
fluid  ounces  of  simple  syrup.  The  resulting  syrup  will  contain 
in  each  fluid  dram  one  grain  ferrous  phosphate,  Fcg  Po  Og ;  one 
grain  quiuic  phosphate,  (Coq  H^i  No  Oo)3  2  H3  P  0^.  and  ^^^nd  part 
of  a  grain  of  strychnine. 

These  two  syrups  afford  good  examples  of  two  classes  of  syrups 
that  present  considerable]  difficulties  in  manij)ulation  with  the  for- 
mulae in  general  use,  which  are  quite  removed  in  the  two  just  sub- 
mitted. Both  have  now  been  tested  on  a  large  scale  for  some  time, 
and  found  very  satisfactory  in  their  products.  No  originality  is 
claimed  in  the  use  of  metallic  iron  in  place  of  precipitated  ferrous 
phosphate.  It  was  first  suggested  by  Mr.  H.  W.  Jones,  in  the 
columns  of  the  Pharmacutical  Journal.  The  chief  point  is  the  im- 
portance of  using  tribasic  (ortho)  phosphoric  acid,  H.,  PO^;  both 
metaphosphoric  acid,  H  P  O3,  and  pyrophosphoric  acid  Hj  Po  0^,  if 
present  in  the  acid  to  even  a  small  extent,  are  certain  to  cause 
trouble.  The  precaution  given  as  to  filtering  the  solution  of  ferrous 
phosphate  will  be  found  useful  in  many  other  cases.  A  beaker  full 
of  solution  of  ferrous  iodide  filtered  in  a  similar  manner,  Avith  a 
layer  of  syrup  the  eighth  of  an  inch  thick  floating  on  the  surface, 
can  be  left  exposed  for  twenty-four  hours  without  injury  to  the 
solution.  It  is,  of  course,  necessary  that  the  solution  should  have 
the  greatest  specific  gravity. 

Coloured  Fires.  S.Kern.  (Ghem.  Ne^us,  Sept.  29, 1876.)  In  pre- 
paring coloured  fires  for  fireworks  according  to  the  usual  formulse 


314 


YEAR-BOOK    OF    PHARMACY. 


given  in  manuals  of  pyrotechiiy,  it  is  often  important  to  know  the 
speed  with  which  they  burn ;  as  in  some  cases,  such  as  decorations 
and  lances,  they  should  bum  slowly ;  whereas  in  others,  such  as 
wheels,  stars  for  rockets,  and  Roman  candles,  they  ought  to  burn 
quicker.  The  following  tables  are  so  arranged  that  every  formula 
with  a  higher  number  yields  a  slower  burning  mixture  than  one 
with  a  lower  number.  Thus,  No.  5  burns  quicker  than  No.  6,  and 
slower  than  No.  4, 

Chreeii- coloured  Fires. 


No. 

Potassium  Chlorate 

Barium  Nitrate 

Sulphur  per 

per  cent. 

per  cent. 

cent. 

1. 

36 

40 

24 

2. 

29 

48 

23 

3. 

24 

53 

23 

4. 

21 

57 

22 

6. 

18 

60 

22 

6. 

16 

f)2 

22 

7. 

14 

64 

22 

8. 

13 

66 

21 

9. 

12 

67 

21 

10. 

11 

68 

21 

11. 

10 

69 

21 

12. 

95 

69-5 

21 

13. 

9 

70 

21 

14. 

8-5 

70-5 

21 

15. 

8 

71 

21 

Red-coloured  Fires. 


No. 

Potassium 
Chlorate 
per  cent. 

Strontium 

Nitrate 
per  cent. 

Sulphur 
per  cent. 

Carbon  Powder 
per  cent. 

1. 

40 

39 

18 

3 

2. 

32 

46 

19 

2 

3. 

27 

51 

20 

2 

4. 

23 

55 

20 

2 

5. 

20 

58 

20-5 

1-5 

6. 

18 

60 

21 

7. 

16 

61-6 

21-2 

1-2 

8. 

15 

63 

21 

9. 

13 

64 

22 

10. 

12 

65 

22 

11. 

11 

66 

22 

12. 

10 

67 

22 

13. 

10 

67-25 

22 

0-75 

14. 

9-25 

68 

22 

0-75 

15. 

9 

68-35 

22 

o-e.'^ 

NOTES   AND    FORMULAE. 
Violet- coloured  Fires. 


;i5 


Potassium 

Calcium 

Malachite 

Sulphur 
per  cent. 

No. 

Chlorate 

Carbonate 

Powdered 

per  cent. 

per  cent. 

per  cent. 

1. 

52 

29 

4 

15 

2. 

52 

28 

5 

15 

3. 

52 

26 

7 

15 

4. 

52 

24 

9 

15 

5. 

52 

23 

10 

15 

6. 

52 

21 

13 

15 

7. 

51 

20 

14 

15 

8. 

51 

18 

16 

15 

9. 

51 

16 

18 

15 

10. 

51 

15 

19 

15 

11. 

51 

13 

21 

15 

12. 

51 

11 

23 

15 

13. 

51 

10 

24 

15 

14. 

51 

8 

26 

15 

15. 

51 

6 

28 

15 

Influence  of  Bottles  on  Wine.  (Pharmaceut.  Gentralhalle,  1877, 
126.)  Wine  of  excellent  quality  has  been  observed  to  go  bad  in 
consequence  of  its  action  on  the  glass  of  the  bottles  in  which  it 
is  kept.  The  glass  in  such  a  case  ceases  to  be  transparent.  This 
observation  has  been  confirmed  by  an  investigation  carried  out 
by  competent  chemists  at  the  instigation  of  the  Chamber  of  Com- 
merce at  Bordeaux.  From  their  report  it  appears  that  a  good 
bottle  glass,  fully  resisting  the  action  of  the  wine,  has  the  following 
chemical  composition  : — 


Silica 

.     58-4  per  cent 

Potash  and  Soda 

•     11-7 

Alumina  and  Oxide  of  Iron 

•     11-0 

Lime 

.     18-6 

The  glass  which  had  proved  injurious  to  the  wine  was  found  to 
contain  : — 


Silica        .... 
Potash  and  Soda 
Alumina  and  Oxide  of  Iron 
Lime         .... 


52*4  per  cent. 
4-4 
11-1 
32-1 


The  acids  of  the  wine  appear  to  act  principally  upon  the  lime. 
The  best  glass  contains  18  to  20  per  cent,  of  lime  to  59-60  per  cent, 
of  silica ;  the  worst  25  to  30  per  cent,  of  lime  to  50-52  per  cent,  of 
silica.  In  bottles  of  the  latter  composition  the  wine  soon  becomes 
thick  and  tasteless. 


316  YEAR-BOOK    OP    PHARMACY. 

Phenicated  Camphor.  (Phann.  Jourv.,  .3rd  series,  vii.,  7t)^\  and 
Journal  de  FJiarmncie  [4],  xxv.,  32,  from  the  BulJefin  Thempeutique.) 
The  preparation  which  has  been  introduced  by  Dr.  Soulez  under 
this  name  is  a  simple  solution  of  2|  parts  of  camphor  in  1  part 
of  carbolic  acid.  The  liquid  thus  obtained  is  pale  yellow,  of  an 
oleaginous  consistency,  and  smells  slightly  of  camphor,  without  any 
admixture  of  the  carbolic  odour.  Plienicated  camphor  is  insoluble 
in  water,  in  glycerin,  and  in  alcohol ;  but  it  dissolves  in  all  pro- 
portions in  the  fat  oils  (olive  and  almond),  and  readily  emulsifies 
with  water  containing  saponin. 

This  preparation  is  recommended  by  Dr.  Soulez  as  a  preventive 
of  fermentation  in  dressings  for  wounds.  The  dressings  are  steeped 
in  a  mixture  of  10  parts  of  phenicated  camphor  and  200  parts  of 
olive  oil,  or  one  of  10  parts  of  phenicated  camphor  and  200  parts 
(if  infusion  of  saponaria.  The  infusion  may  be  prepared  by  pouring 
1000  parts  of  boiling  water  upon  100  parts  of  saponaria  leaves. 
Dr.  Soulez,  however,  prefers  to  make  a  tincture  by  macerating  250 
grams  of  Quillaia  saponaria  bark  for  ten  days  in  a  litre  of  90° 
alcohol.  This  tincture,  mixed  with  its  weight  of  phenicated  cam- 
phor, forms  a  concentrated  emulsion,  which  is  diluted  with  ten 
|)arts  of  water  when  required  for  use. 

Cod  Liver  Oil  and  Ferrous  Iodide.  The  following  formiila  for 
this  preparation  has  been  published  in  the  Nieu  Zi/ihchrift  voor  de 
Pharmacie  in  Ncderland,  by  a  commission  which  the  Netherlands 
Pharmaceutical  Society  has  appointed  to  examine  secret  remedies 
and  specialities:  — 

P>     Iodine        ...         ....       1  part. 

Pulverized  Iron  .....       1  part. 

Pale  Cod  Liver  Oil 80  parts. 

Triturate  the  pulverized  iron  in  a  mortar  with  the  iodine  and 
one-fourth  of  the  oil,  and  heat  the  mixture  in  a  water  batli  with 
continual  stirring,  until  the  brown  colour  of  the  iodine  has  entirely 
disappeared  and  given  place  to  a  deep  purple  colour,  showing  that 
the  ferrous  iodide  has  been  formed  and  dissolved.  Then  add  the 
remainder  of  the  oil,  mix  carefully,  and  after  standing  decant  into 
dry  bottles,  which  are  to  bo  completely  filled,  closed  immediately, 
and  kept  sheltei-ed  from  the  light. 

This  oil  is  of  a  purple  colour,  and  differs  in  taste  but  little  from 
the  ordinary  medicinal  cod  liver  oil.  Exposed  to  the  light  it  changes 
after  a  few  days  to  a  red-brown  colour.  Although  the  taste  is  but 
little  altered,  it  is  important  to  prevent  this  change  of  colour  which 


I 


NOTES   AND    FORMULA.  -317 

always  indicates  the  liberation  of  iodine.  In  well-stoppered  bottles 
the  oil  remains  unaltered ;  but  it  is  as  well  not  to  prepare  too  much  in 
advance.  The  taste  and  colour  furnish  good  criteria  for  its  condition. 
Syrup  of  Liquorice  Koot.  A.  P.  Brown.  (From  a  paper  read 
in  the  Philadelphia  College  of  Pharmacy,  October  7th :  Amer. 
Journ.  Phann.,  Nov.,  1876,  487.)  Having  had  occasion  to  prepare 
some  ammoniacal  glycjrrhizin,  it  occurred  to  the  author  that  the 
use  of  ammonia  in  preparing  syrup  of  liquorice  root  might  be  an 
advantage.     He  therefore  devised  the  following  formula  : — 

1^  Liquorice  Eoot  ....  4  troy  ounces. 
Cold  Water  ....  sufficient  quantity. 
Solution  of  Ammonia  ...  1  fluid  ouuce. 
Granulated  Sugar   .         .         .         .13  troy  ounces. 

Grind  the  root  in  a  mill,  and  place  it  in  a  wide-mouth  bottle,  with 
a  tightly  fitting  stopper ;  pour  upon  it  one  pint  of  water  mixed  with 
the  solution  of  ammonia  ;  macerate  for  forty-eight  hours  ;  then  trans- 
fer it  to  a  funnel,  and  allow  the  liquid  to  drain  from  it,  and  add  suffi- 
cient water  until  two  pints  of  hquid  has  passed  ;  allow  it  to  stand 
until  the  particles  have  subsided,  then  decant  and  evaporate  to 
eiglit  fluid  ounces  ;  filter,  and  having  added  the  sugar,  dissolve  it 
with  the  aid  of  heat. 

Experiments  were  made  with  the  ordinary  liquorice  root  and  the 
Russian  peeled  root,  and  of  the  two  the  syrup  made  from  the 
Russian  root  was  decidedly  the  finest.  The  cortical  portion  of 
liquorice  root  is  acrid,  without  possessing  the  peculiar  virtues  of 
the  root ;  the  Russian  root,  being  deprived  of  the  epidermis,  will 
therefore  make  the  best  preparation. 

The  syrup  thus  prepared  is  of  a  dark  brown  colour,  and  contains 
all  the  sweet  principles  of  the  root  without  the  starch  and  other 
inert  matter.  Sulphate  of  magnesium,  iodide  and  bromide  of 
potassium  lose  most  of  their  taste  when  mixed  with  this  syrup. 

The  author  said  he  had  also  made  and  used  ammoniacal  glycyr- 
rhizin  to  mask  the  bitter  taste  of  quinine  ;  two  drams  of  the  glycyr- 
rhizin  are  dissolved  in  one  pint  of  syrup,  then  to  each  fluid  dram 
is  added  one  grain  of  quinine  sulphate.  In  making  ammoniacal 
glycyrrhizin  care  must  be  observed  to  use  chemically  pure  sulphuric 
acid  in  the  precipitation ;  and  in  the  preparation  of  the  compound 
mixture  of  liquorice  by  the  process  suggested,  an  excess  of  ammonia 
must  be  avoided. 

The  author  has  also  prepared  a  brown  mixture  from  liquorice 
root  and  ammonia  by  the  following  process  : — 


MS  YEAR-BOOK    OF    PHARMACY. 

5t  Liquorice  Eoot  ...  .4  troy  ounces. 
Water  of  Ammonia  .  .  .  .  1  fluid  ounce. 
Water sufficient  quantity. 

Proceed  in  the  same  manner  as  for  syrup  of  liquorice  root,  but 
in.stead  of  evaporating  to  eight  fluid  ounces,  evaporate  to  twelve 
tiuid  ounces,  and  mix  this  with  the  gum  arable,  suy;ar,  and  other 
ingredients.  Lastly,  add  water  of  ammonia  until  a  clear  solution  is 
obtained,  taking  care  not  to  add  an  excess.  Brown  mixture,  pre- 
pared by  the  above  process,  is  of  a  brownish  yellow  colour,  and 
almost  entirely  free  from  sediment. 

Croton  Oil  Pencils.  M.  Limousin.  (Eepert.  de  Pharm.,  1877, 
129.)  For  the  local  application  of  croton  oil  the  author  recom- 
mends the  use  of  pencils  made  according  to  the  following  formula  : 
—  Two  parts  of  croton  oil  are  added  to  one  of  cacao  butter  and  one 
of  white  wax,  melted  over  the  water  bath  :  when  the  mixture  begins 
to  cool  it  is  poured  into  cylindrical  moulds,  in  which  it  soon  solidi- 
fies. Although  the  pencil  only  contains  50  per  cent,  of  oil,  still, 
owing  to  the  avoidance  of  all  loss  through  volatilization,  the  revul- 
sive action  of  the  drug  is  found  to  be  even  more  powerful  in  this 
form  than  in  its  natural  condition,  and  it  has  been  successfully  em- 
ployed with  the  view  of  obtaining  this  action  by  Dr.  Jules  Simon  at 
the  Hopital  des  Enfants  Malades.  Dr.  Lailler  has  used  these  pencils 
in  the  treatment  of  tinea  tonsurans.  The  pencils  seem  to  retain 
their  properties  for  several  months. 

Sjrrup  of  Coffee.  R.  H.  Bernhardt.  (Druggists'  Circular  and 
Chemical  Gazette,  Sept.,  1876.)  The  preparation  of  this  elegant 
syrup  has  long  been  within  the  province  of  the  pharmaceutist ;  yet 
with  all  the  various  formulae  for  its  production  contributed  from 
time  to  time,  it  has  not  yet  attained  any  appreciable  degree  of  per- 
fection. Its  liability  to  fermentation  has  continually  been  a  barrier 
to  its  more  general  adoption. 

Syrup  of  coffee,  like  some  other  officinal  syrups,  is  possessed  of 
little  or  no  medicinal  value.  Its  importance  as  a  pharmaceutical 
preparation  lies  exclusively  in  its  remarkable  power  of  disguising 
tbe  taste  of  nauseous  medicines,  and  the  delicate  flavour  it  imparts 
as  an  adjunct  or  diluent. 

The  following  formula,  in  which  is  used  the  process  known  as 
"  cold  percolation,"  has  been  found  after  many  experiments  the 
most  appropriate  : — 

JL    Roasted  Coffee   ....  2  troy  ounces. 

Crushed  Sugar  ....  28  troy  ounces. 

Distilled  Water  ....    sufficient  quantity. 


NOTES    AND    FORMUL.?;.  319 

Moisten  the  coffee,  previously  reduced  to  a  moderately  fine  powder, 
with  half  a  fluid  ounce  of  distilled  water ;  introduce  it  into  a  conical 
glass  percolator,  and  gradually  pour  distilled  water  upon  it  until 
sixteen  fluid  ounces  of  infusion  have  passed.  Add  this  to  the  sugar 
contained  in  a  glass  percolator,  in  the  oriflee  of  which  a  piece  ot 
soft  sponge  has  been  introduced ;  and  in  order  to  prevent  the 
itrimediate  escape  of  the  liquid,  a  cork  is  to  be  tightly  fitted  in  the 
rube  of  the  percolator  at  the  bottom.  The  whole  is  tlien  to  be  closely 
covered  and  set  aside  for  about  two  hours,  or  until  the  sugar  has 
dissolved  down  to  half  its  former  bulk.  Then  the  cork  can  be 
removed  and  the  liquid  allowed  to  drop.  If  the  liquid  has  all 
[)assed  and  there  still  remains  a  quantity  of  undissolved  sugar  in 
the  percolator,  pour  it  again  upon  the  sugar  until  the  desired  result 
is  effected.  This  last  proceeding  is,  however,  entirely  unnecessary, 
and  only  occupies  time ;  an  essential  precaution  (and  in  this  simple 
mechanical  contrivance  depends  the  success  of  the  entire  process)  is 
to  carefully  insert  the  sponge  in  the  orifice,  not  too  tightly,  but  also 
not  too  loosely — just  sufficiently  close  to  allow  the  syrup  to  ^sass  drop 
hy  drop. 

It  is  also  requisite  to  the  immediate  transparency  of  the  prepar- 
ation, that  the  infusion  obtained  by  percolation  should  be  perfectly 
clear.  To  accomplish  this  in  the  quickest  and  most  convenient  man- 
ner, it  is  only  necessary  to  close  the  orifice  of  the  percolator  with  a 
wad  of  dry,  well  compressed  cotton,  tightly  inserted.  It  will  be 
noticed  that  there  is  not  the  slightest  degree  of  heat  used  in  prepar- 
ing this  delicious  syrup,  further  than  in  the  parching  of  the  cofiee ; 
and  the  transparency,  reliability,  and  beauty  of  the  product  can- 
not be  surpassed  by  any  generally  known  formula. 

The  strength  of  this  preparation  can  be  made  as  individual  fancy 
or  desire  may  dictate.  The  above  afi'ords  a  very  handsome  dark 
brown  coloured  liquid,  pretty  well  impregnated  with  the  odour  of 
coffee;  and  for  ordinary  purposes  serves  exceedingly  well.  For  dis- 
guising the  bitter  taste  of  alkaloids,  etc.,  the  writer  recommends  a 
preparation  double  the  strength  of  the  above  ;  this  is  easily  obtained 
by  simply  substituting  twice  the  amount  (4  troy  ounces)  of  coffee, 
and  treating  as  directed  in  the  general  formula. 

Fluid  Extract  of  Jaborandi.  F.  V.  Greene.  {Amer.  Joum. 
Pharm.,  1877,  395.) 

9>  Jaborandi  leaves,  in  moderately  fine 

powder 16  troy  ounces. 

Alcohol  (50  per  cent.)      .         .        sufficient  quantity. 


820  YEAR-BOOK    OF    PHARMACY. 

Moisten  the  powder  thoroughly  with  the  menstruum,  pack  in  a 
conical  glass  percolator